Monsoon

From Wikipedia, the free encyclopedia

 

Advancing monsoon clouds and showers in Aralvaimozhy, near Nagercoil, India

 

Monsoon (/mɒnˈsuːn/) is traditionally defined as a seasonal reversing wind accompanied by corresponding changes in precipitation, but is now used to describe seasonal changes in atmospheric circulation and precipitation associated with the asymmetric heating of land and sea. Usually, the term monsoon is used to refer to the rainy phase of a seasonally changing pattern, although technically there is also a dry phase. The term is sometimes incorrectly used for locally heavy but short-term rains, although these rains meet the dictionary definition of monsoon.

The major monsoon systems of the world consist of the West African and Asia-Australian monsoons. The inclusion of the North and South American monsoons with incomplete wind reversal has been debated.

The term was first used in English in British India and neighbouring countries to refer to the big seasonal winds blowing from the Bay of Bengal and Arabian Sea in the southwest bringing heavy rainfall to the area.

Etymology

Monsoon clouds over Lucknow, Uttar Pradesh, India

 

The etymology of the word monsoon is not wholly certain. The English monsoon came from Portuguese monção, ultimately from Arabic mawsim (موسم "season"), "perhaps partly via early modern Dutch monson."

History

Strengthening of the Asian monsoon has been linked to the uplift of the Tibetan Plateau after the collision of the Indian sub-continent and Asia around 50 million years ago. Because of studies of records from the Arabian Sea and that of the wind-blown dust in the Loess Plateau of China, many geologists believe the monsoon first became strong around 8 million years ago. More recently, studies of plant fossils in China and new long-duration sediment records from the South China Sea led to a timing of the monsoon beginning 15–20 million years ago and linked to early Tibetan uplift. Testing of this hypothesis awaits deep ocean sampling by the Integrated Ocean Drilling Program. The monsoon has varied significantly in strength since this time, largely linked to global climate change, especially the cycle of the Pleistocene ice ages. A study of marine plankton suggested that the Indian Monsoon strengthened around 5 million years ago. Then, during ice periods, the sea level fell and the Indonesian Seaway closed. When this happened, cold waters in the Pacific were impeded from flowing into the Indian Ocean. It is believed that the resulting increase in sea surface temperatures in the Indian Ocean increased the intensity of monsoons.

Five episodes during the Quaternary at 2.22 Ma (PL-1), 1.83 Ma (PL-2), 0.68 Ma (PL-3), 0.45 Ma (PL-4) and 0.04 Ma (PL-5) were identified which showed a weakening of Leeuwin Current (LC). The weakening of the LC would have an effect on the sea surface temperature (SST) field in the Indian Ocean, as the Indonesian through flow generally warms the Indian Ocean. Thus these five intervals could probably be those of considerable lowering of SST in the Indian Ocean and would have influenced Indian monsoon intensity. During the weak LC, there is the possibility of reduced intensity of the Indian winter monsoon and strong summer monsoon, because of change in the Indian Ocean dipole due to reduction in net heat input to the Indian Ocean through the Indonesian through flow. Thus a better understanding of the possible links between El Niño, Western Pacific Warm Pool, Indonesian Throughflow, wind pattern off western Australia, and ice volume expansion and contraction can be obtained by studying the behaviour of the LC during Quaternary at close stratigraphic intervals.

Strength of impact

On May 28, in the dry season

 

On August 28, in the rainy season,Western Ghats in 2010

 

The impact of monsoon on the local weather is different from place to place. In some places there is just a likelihood of having a little more or less rain. In other places, quasi semi-deserts are turned into vivid green grasslands where all sorts of plants and crops can flourish. 

The Indian Monsoon turns large parts of India from a kind of semi-desert into green lands. See photos only taken 3 months apart in the Western Ghats. In places like this it is crucial for farmers to have the right timing for putting the seeds on the fields, as it is essential to use all the rain that is available for growing crops.

Process

Monsoons are large-scale sea breezes  which occur when the temperature on land is significantly warmer or cooler than the temperature of the ocean. These temperature imbalances happen because oceans and land absorb heat in different ways. Over oceans, the air temperature remains relatively stable for two reasons: water has a relatively high heat capacity (3.9 to 4.2 J g⁻¹ K⁻¹), and because both conduction and convection will equilibrate a hot or cold surface with deeper water (up to 50 metres). In contrast, dirt, sand, and rocks have lower heat capacities (0.19 to 0.35 J g⁻¹ K⁻¹), and they can only transmit heat into the earth by conduction and not by convection. Therefore, bodies of water stay at a more even temperature, while land temperature are more variable.

During warmer months sunlight heats the surfaces of both land and oceans, but land temperatures rise more quickly. As the land's surface becomes warmer, the air above it expands and an area of low pressure develops. Meanwhile, the ocean remains at a lower temperature than the land, and the air above it retains a higher pressure. This difference in pressure causes sea breezes to blow from the ocean to the land, bringing moist air inland. This moist air rises to a higher altitude over land and then it flows back toward the ocean (thus completing the cycle). However, when the air rises, and while it is still over the land, the air cools. This decreases the air's ability to hold water, and this causes precipitation over the land. This is why summer monsoons cause so much rain over land.

In the colder months, the cycle is reversed. Then the land cools faster than the oceans and the air over the land has higher pressure than air over the ocean. This causes the air over the land to flow to the ocean. When humid air rises over the ocean, it cools, and this causes precipitation over the oceans. (The cool air then flows towards the land to complete the cycle.) 

Most summer monsoons have a dominant westerly component and a strong tendency to ascend and produce copious amounts of rain (because of the condensation of water vapor in the rising air). The intensity and duration, however, are not uniform from year to year. Winter monsoons, by contrast, have a dominant easterly component and a strong tendency to diverge, subside and cause drought.

Similar rainfall is caused when moist ocean air is lifted upwards by mountains, surface heating, convergence at the surface, divergence aloft, or from storm-produced outflows at the surface. However the lifting occurs, the air cools due to expansion in lower pressure, and this produces condensation.

Global monsoon

Africa (West African and Southeast African)

Southeast African moonsoon clouds, over Mayotte island.

 

The monsoon of western Sub-Saharan Africa is the result of the seasonal shifts of the Intertropical Convergence Zone and the great seasonal temperature and humidity differences between the Sahara and the equatorial Atlantic Ocean. It migrates northward from the equatorial Atlantic in February, reaches western Africa on or near June 22, then moves back to the south by October. The dry, northeasterly trade winds, and their more extreme form, the harmattan, are interrupted by the northern shift in the ITCZ and resultant southerly, rain-bearing winds during the summer. The semiarid Sahel and Sudan depend upon this pattern for most of their precipitation.

North America

Incoming monsoon clouds over Phoenix, Arizona

 

The North American monsoon (NAM) occurs from late June or early July into September, originating over Mexico and spreading into the southwest United States by mid-July. It affects Mexico along the Sierra Madre Occidental as well as Arizona, New Mexico, Nevada, Utah, Colorado, West Texas and California. It pushes as far west as the Peninsular Ranges and Transverse Ranges of Southern California, but rarely reaches the coastal strip (a wall of desert thunderstorms only a half-hour's drive away is a common summer sight from the sunny skies along the coast during the monsoon). The North American monsoon is known to many as the Summer, Southwest, Mexican or Arizona monsoon. It is also sometimes called the Desert monsoon as a large part of the affected area are the Mojave and Sonoran deserts. However, it is debatable whether the North and South American weather patterns with incomplete wind reversal should be counted as true monsoons.

Asia

The Asian monsoons may be classified into a few sub-systems, such as the Indian Subcontinental Monsoon which affects the Indian subcontinent and surrounding regions including Nepal, and the East Asian Monsoon which affects southern China, Taiwan, Korea and parts of Japan.

South Asian monsoon

Southwest monsoon

Onset dates and prevailing wind currents of the southwest summer monsoons in India

 

The southwestern summer monsoons occur from July through September. The Thar Desert and adjoining areas of the northern and central Indian subcontinent heat up considerably during the hot summers. This causes a low pressure area over the northern and central Indian subcontinent. To fill this void, the moisture-laden winds from the Indian Ocean rush into the subcontinent. These winds, rich in moisture, are drawn towards the Himalayas. The Himalayas act like a high wall, blocking the winds from passing into Central Asia, and forcing them to rise. As the clouds rise, their temperature drops, and precipitation occurs. Some areas of the subcontinent receive up to 10,000 mm (390 in) of rain annually. 

The southwest monsoon is generally expected to begin around the beginning of June and fade away by the end of September. The moisture-laden winds on reaching the southernmost point of the Indian Peninsula, due to its topography, become divided into two parts: the Arabian Sea Branch and the Bay of Bengal Branch. 

The Arabian Sea Branch of the Southwest Monsoon first hits the Western Ghats of the coastal state of Kerala, India, thus making this area the first state in India to receive rain from the Southwest Monsoon. This branch of the monsoon moves northwards along the Western Ghats (Konkan and Goa) with precipitation on coastal areas, west of the Western Ghats. The eastern areas of the Western Ghats do not receive much rain from this monsoon as the wind does not cross the Western Ghats. 

The Bay of Bengal Branch of Southwest Monsoon flows over the Bay of Bengal heading towards North-East India and Bengal, picking up more moisture from the Bay of Bengal. The winds arrive at the Eastern Himalayas with large amounts of rain. Mawsynram, situated on the southern slopes of the Khasi Hills in Meghalaya, India, is one of the wettest places on Earth. After the arrival at the Eastern Himalayas, the winds turns towards the west, travelling over the Indo-Gangetic Plain at a rate of roughly 1–2 weeks per state, pouring rain all along its way. June 1 is regarded as the date of onset of the monsoon in India, as indicated by the arrival of the monsoon in the southernmost state of Kerala.

The monsoon accounts for nearly 80% of the rainfall in India. Indian agriculture (which accounts for 25% of the GDP and employs 70% of the population) is heavily dependent on the rains, for growing crops especially like cotton, rice, oilseeds and coarse grains. A delay of a few days in the arrival of the monsoon can badly affect the economy, as evidenced in the numerous droughts in India in the 1990s. 

The monsoon is widely welcomed and appreciated by city-dwellers as well, for it provides relief from the climax of summer heat in June. However, the roads take a battering every year. Often houses and streets are waterlogged and slums are flooded despite drainage systems. A lack of city infrastructure coupled with changing climate patterns causes severe economic loss including damage to property and loss of lives, as evidenced in the 2005 flooding in Mumbai that brought the city to a standstill. Bangladesh and certain regions of India like Assam and West Bengal, also frequently experience heavy floods during this season. Recently, areas in India that used to receive scanty rainfall throughout the year, like the Thar Desert, have surprisingly ended up receiving floods due to the prolonged monsoon season.

The influence of the Southwest Monsoon is felt as far north as in China's Xinjiang. It is estimated that about 70% of all precipitation in the central part of the Tian Shan Mountains falls during the three summer months, when the region is under the monsoon influence; about 70% of that is directly of "cyclonic" (i.e., monsoon-driven) origin (as opposed to "local convection").

Northeast monsoon

Monsoon clouds in Kolkata

 

Around September, with the sun fast retreating south, the northern land mass of the Indian subcontinent begins to cool off rapidly. With this air pressure begins to build over northern India, the Indian Ocean and its surrounding atmosphere still holds its heat. This causes cold wind to sweep down from the Himalayas and Indo-Gangetic Plain towards the vast spans of the Indian Ocean south of the Deccan peninsula. This is known as the Northeast Monsoon or Retreating Monsoon. 

While travelling towards the Indian Ocean, the dry cold wind picks up some moisture from the Bay of Bengal and pours it over peninsular India and parts of Sri Lanka. Cities like Chennai, which get less rain from the Southwest Monsoon, receive rain from this Monsoon. About 50% to 60% of the rain received by the state of Tamil Nadu is from the Northeast Monsoon. In Southern Asia, the northeastern monsoons take place from October to December when the surface high-pressure system is strongest. The jet stream in this region splits into the southern subtropical jet and the polar jet. The subtropical flow directs northeasterly winds to blow across southern Asia, creating dry air streams which produce clear skies over India. Meanwhile, a low pressure system known as a monsoon trough develops over South-East Asia and Australasia and winds are directed toward Australia.

East Asian Monsoon

The East Asian monsoon affects large parts of Indo-China, Philippines, China, Taiwan, Korea and Japan. It is characterised by a warm, rainy summer monsoon and a cold, dry winter monsoon. The rain occurs in a concentrated belt that stretches east-west except in East China where it is tilted east-northeast over Korea and Japan. The seasonal rain is known as Meiyu in China, Jangma in Korea, and Bai-u in Japan, with the latter two resembling frontal rain. 

The onset of the summer monsoon is marked by a period of premonsoonal rain over South China and Taiwan in early May. From May through August, the summer monsoon shifts through a series of dry and rainy phases as the rain belt moves northward, beginning over Indochina and the South China Sea (May), to the Yangtze River Basin and Japan (June) and finally to North China and Korea (July). When the monsoon ends in August, the rain belt moves back to South China.

Australia

Monsoonal squall nears Darwin, Northern Territory, Australia

 

Also known as the Indo-Australian Monsoon. The rainy season occurs from September to February and it is a major source of energy for the Hadley circulation during boreal winter. The Maritime Continent Monsoon and the Australian Monsoon may be considered to be the same system, the Indo-Australian Monsoon. 

It is associated with the development of the Siberian High and the movement of the heating maxima from the Northern Hemisphere to the Southern Hemisphere. North-easterly winds flow down Southeast Asia, are turned north-westerly/westerly by Borneo topography towards Australia. This forms a cyclonic circulation vortex over Borneo, which together with descending cold surges of winter air from higher latitudes, cause significant weather phenomena in the region. Examples are the formation of a rare low-latitude tropical storm in 2001, Tropical Storm Vamei, and the devastating flood of Jakarta in 2007. 

The onset of the monsoon over the Maritime Continent tends to follow the heating maxima down Vietnam and the Malay Peninsula (September), to Sumatra, Borneo and the Philippines (October), to Java, Sulawesi (November), Irian Jaya and Northern Australia (December, January). However, the monsoon is not a simple response to heating but a more complex interaction of topography, wind and sea, as demonstrated by its abrupt rather than gradual withdrawal from the region. The Australian monsoon (the "Wet") occurs in the southern summer when the monsoon trough develops over Northern Australia. Over three-quarters of annual rainfall in Northern Australia falls during this time.

Europe

The European Monsoon (more commonly known as the return of the westerlies) is the result of a resurgence of westerly winds from the Atlantic, where they become loaded with wind and rain. These westerly winds are a common phenomenon during the European winter, but they ease as spring approaches in late March and through April and May. The winds pick up again in June, which is why this phenomenon is also referred to as "the return of the westerlies".

The rain usually arrives in two waves, at the beginning of June and again in mid- to late June. The European monsoon is not a monsoon in the traditional sense in that it doesn't meet all the requirements to be classified as such. Instead the return of the westerlies is more regarded as a conveyor belt that delivers a series of low pressure centres to Western Europe where they create unsettled weather. These storms generally feature significantly lower than average temperatures, fierce rain or hail, thunder and strong winds.

The return of the westerlies affects Europe's Northern Atlantic coastline, more precisely Ireland, Great Britain, the Benelux countries, Western Germany, Northern France and parts of Scandinavia.

Hypervalent molecule

From Wikipedia, the free encyclopedia

 

A hypervalent molecule (the phenomenon is sometimes colloquially known as expanded octet) is a molecule that contains one or more main group elements apparently bearing more than eight electrons in their valence shells. Phosphorus pentachloride (PCl₅), sulfur hexafluoride (SF₆), chlorine trifluoride (ClF₃), the chlorite (ClO₂⁻) ion, and the triiodide (I₃⁻) ion are examples of hypervalent molecules.

Definitions and nomenclature

Hypervalent molecules were first formally defined by Jeremy I. Musher in 1969 as molecules having central atoms of group 15–18 in any valence other than the lowest (i.e. 3, 2, 1, 0 for Groups 15, 16, 17, 18 respectively, based on the octet rule).

Several specific classes of hypervalent molecules exist:

• Hypervalent iodine compounds are useful reagents in organic chemistry (e.g. Dess–Martin periodinane)
• Tetra-, penta- and hexavalent phosphorus, silicon, and sulfur compounds (ex. PCl₅, PF₅, SF₆, sulfuranes and persulfuranes)
• Noble gas compounds (ex. xenon tetrafluoride, XeF₄)
• Halogen polyfluorides (ex. ClF₅)

N-X-L notation

N-X-L nomenclature, introduced collaboratively by the research groups of Martin, Arduengo, and Kochi in 1980, is often used to classify hypervalent compounds of main group elements, where:

• N represents the number of valence electrons
• X is the chemical symbol of the central atom
• L the number of ligands to the central atom

Examples of N-X-L nomenclature include:

• XeF₂, 10-Xe-2
• PCl₅, 10-P-5
• SF₆, 12-S-6
• IF₇, 14-I-7

History and controversy

The debate over the nature and classification of hypervalent molecules goes back to Gilbert N. Lewis and Irving Langmuir and the debate over the nature of the chemical bond in the 1920s. Lewis maintained the importance of the two-center two-electron (2c-2e) bond in describing hypervalence, thus using expanded octets to account for such molecules. Using the language of orbital hybridization, the bonds of molecules like PF₅ and SF₆ were said to be constructed from sp³dⁿ orbitals on the central atom. Langmuir, on the other hand, upheld the dominance of the octet rule and preferred the use of ionic bonds to account for hypervalence without violating the rule (e.g. "SF₄²⁺ 2F⁻" for SF₆). 

In the late 1920s and 1930s, Sugden argued for the existence of a two-center one-electron (2c-1e) bond and thus rationalized bonding in hypervalent molecules without the need for expanded octets or ionic bond character; this was poorly accepted at the time. In the 1940s and 1950s, Rundle and Pimentel popularized the idea of the three-center four-electron bond, which is essentially the same concept which Sugden attempted to advance decades earlier; the three-center four-electron bond can be alternatively viewed as consisting of two collinear two-center one-electron bonds, with the remaining two nonbonding electrons localized to the ligands.

The attempt to actually prepare hypervalent organic molecules began with Hermann Staudinger and Georg Wittig in the first half of the twentieth century, who sought to challenge the extant valence theory and successfully prepare nitrogen and phosphorus-centered hypervalent molecules. The theoretical basis for hypervalency was not delineated until J.I. Musher's work in 1969.

In 1990, Magnusson published a seminal work definitively excluding the significance of d-orbital hybridization in the bonding of hypervalent compounds of second-row elements. This had long been a point of contention and confusion in describing these molecules using molecular orbital theory. Part of the confusion here originates from the fact that one must include d-functions in the basis sets used to describe these compounds (or else unreasonably high energies and distorted geometries result), and the contribution of the d-function to the molecular wavefunction is large. These facts were historically interpreted to mean that d-orbitals must be involved in bonding. However, Magnusson concludes in his work that d-orbital involvement is not implicated in hypervalency.

Nevertheless, a 2013 study showed that although the Pimentel ionic model best accounts for the bonding of hypervalent species, the energetic contribution of an expanded octet structure is also not null. In this modern valence bond theory study of the bonding of xenon difluoride, it was found that ionic structures account for about 81% of the overall wavefunction, of which 70% arises from ionic structures employing only the p orbital on xenon while 11% arises from ionic structures employing an ${\displaystyle \mathrm {sd} _{z^{2}}}$hybrid on xenon. The contribution of a formally hypervalent structure employing an orbital of sp³d hydridization on xenon accounts for 11% of the wavefunction, with a diradical contribution making up the remaining 8%. The 11% sp³d contribution results in a net stabilization of the molecule by 7.2 kcal (30 kJ) mol⁻¹, a minor but significant fraction of the total energy of the total bond energy (64 kcal (270 kJ) mol⁻¹). Other studies have similarly found minor but non-negligible energetic contributions from expanded octet structures in SF₆ (17%) and XeF₆ (14%).

Despite the lack of chemical realism, the IUPAC recommends the drawing of expanded octet structures for functional groups like sulfones and phosphoranes, in order to avoid the drawing of a large number of formal charges or partial single bonds.

Criticism

Both the term and concept of hypervalency still fall under criticism. In 1984, in response to this general controversy, Paul von Ragué Schleyer proposed the replacement of 'hypervalency' with use of the term hypercoordination because this term does not imply any mode of chemical bonding and the question could thus be avoided altogether.

The concept itself has been criticized by Ronald Gillespie who, based on an analysis of electron localization functions, wrote in 2002 that "as there is no fundamental difference between the bonds in hypervalent and non-hypervalent (Lewis octet) molecules there is no reason to continue to use the term hypervalent."

For hypercoordinated molecules with electronegative ligands such as PF₅ it has been demonstrated that the ligands can pull away enough electron density from the central atom so that its net content is again 8 electrons or fewer. Consistent with this alternative view is the finding that hypercoordinated molecules based on fluorine ligands, for example PF₅ do not have hydride counterparts e.g. phosphorane PH₅ which is unknown. 

The ionic model holds up well in thermochemical calculations. It predicts favorable exothermic formation of PF₄⁺F⁻ from phosphorus trifluoride PF₃ and fluorine F₂ whereas a similar reaction forming PH₄⁺H⁻ is not favorable.

Alternative definition

Durrant has proposed an alternative definition of hypervalency, based on the analysis of atomic charge maps obtained from Atoms in molecules theory. This approach defines a parameter called the valence electron equivalent, γ, as “the formal shared electron count at a given atom, obtained by any combination of valid ionic and covalent resonance forms that reproduces the observed charge distribution”. For any particular atom X, if the value of γ(X) is greater than 8, that atom is hypervalent. Using this alternative definition, many species such as PCl₅, SO₄²⁻, and XeF₄, that are hypervalent by Musher's definition, are reclassified as hypercoordinate but not hypervalent, due to strongly ionic bonding that draws electrons away from the central atom. On the other hand, some compounds that are normally written with ionic bonds in order to conform to the octet rule, such as ozone O₃, nitrous oxide NNO, and trimethylamine N-oxide (CH₃)₃NO, are found to be genuinely hypervalent. Examples of γ calculations for phosphate PO₄³⁻ (γ(P) = 2.6, non-hypervalent) and orthonitrate NO₄³⁻ (γ(N) = 8.5, hypervalent) are shown below.

Calculation of the valence electron equivalent for phosphate and orthonitrate

Bonding in hypervalent molecules

Early considerations of the geometry of hypervalent molecules returned familiar arrangements that were well explained by the VSEPR model for atomic bonding. Accordingly, AB₅ and AB₆ type molecules would possess a trigonal bi-pyramidal and octahedral geometry, respectively. However, in order to account for the observed bond angles, bond lengths and apparent violation of the Lewis octet rule, several alternative models have been proposed. 

In the 1950s an expanded valence shell treatment of hypervalent bonding was adduced to explain the molecular architecture, where the central atom of penta- and hexacoordinated molecules would utilize d AOs in addition to s and p AOs. However, advances in the study of ab initio calculations have revealed that the contribution of d-orbitals to hypervalent bonding is too small to describe the bonding properties, and this description is now regarded as much less important. It was shown that in the case of hexacoordinated SF₆, d-orbitals are not involved in S-F bond formation, but charge transfer between the sulfur and fluorine atoms and the apposite resonance structures were able to account for the hypervalency.

Additional modifications to the octet rule have been attempted to involve ionic characteristics in hypervalent bonding. As one of these modifications, in 1951, the concept of the 3-center 4-electron (3c-4e) bond, which described hypervalent bonding with a qualitative molecular orbital, was proposed. The 3c-4e bond is described as three molecular orbitals given by the combination of a p atomic orbital on the central atom and an atomic orbital from each of the two ligands on opposite sides of the central atom. Only one of the two pairs of electrons is occupying a molecular orbital that involves bonding to the central atom, the second pair being non-bonding and occupying a molecular orbital composed of only atomic orbitals from the two ligands. This model in which the octet rule is preserved was also advocated by Musher.

Qualitative model for a three-center four-electron bond

Molecular orbital theory

A complete description of hypervalent molecules arises from consideration of molecular orbital theory through quantum mechanical methods. A LCAO in, for example, sulfur hexafluoride, taking a basis set of the one sulfur 3s-orbital, the three sulfur 3p-orbitals, and six octahedral geometry symmetry-adapted linear combinations (SALCs) of fluorine orbitals, a total of ten molecular orbitals are obtained (four fully occupied bonding MOs of the lowest energy, two fully occupied intermediate energy non-bonding MOs and four vacant antibonding MOs with the highest energy) providing room for all 12 valence electrons. This is a stable configuration only for SX₆ molecules containing electronegative ligand atoms like fluorine, which explains why SH₆ is not a stable molecule. In the bonding model, the two non-bonding MOs (1e_g) are localized equally on all six fluorine atoms.

Valence bond theory

For hypervalent compounds in which the ligands are more electronegative than the central, hypervalent atom, resonance structures can be drawn with no more than four covalent electron pair bonds and completed with ionic bonds to obey the octet rule. For example, in phosphorus pentafluoride (PF₅), 5 resonance structures can be generated each with four covalent bonds and one ionic bond with greater weight in the structures placing ionic character in the axial bonds, thus satisfying the octet rule and explaining both the observed trigonal bipyramidal molecular geometry and the fact that the axial bond length (158 pm) is longer than the equatorial (154 pm).

Phosphorus pentafluoride. There are 2 structures with an axial ionic bond, plus 3 structures with an equatorial ionic bond.

 

For a hexacoordinate molecule such as sulfur hexafluoride, each of the six bonds is the same length. The rationalization described above can be applied to generate 15 resonance structures each with four covalent bonds and two ionic bonds, such that the ionic character is distributed equally across each of the sulfur-fluorine bonds. 

Sulfur hexafluoride. There are 12 structures with the two ionic bonds in adjacent (cis) positions, plus 3 structures with the two ionic bonds in opposite (trans) positions.

 

Spin-coupled valence bond theory has been applied to diazomethane and the resulting orbital analysis was interpreted in terms of a chemical structure in which the central nitrogen has five covalent bonds.

Chemical formula of diazomethane, showing hypervalent nitrogen

 

This led the authors to the interesting conclusion that "Contrary to what we were all taught as undergraduates, the nitrogen atom does indeed form five covalent linkages and the availability or otherwise of d-orbitals has nothing to do with this state of affairs."

Structure, reactivity, and kinetics

Structure

Hexacoordinated phosphorus

Hexacoordinate phosphorus molecules involving nitrogen, oxygen, or sulfur ligands provide examples of Lewis acid-Lewis base hexacoordination. For the two similar complexes shown below, the length of the C-P bond increases with decreasing length of the N-P bond; the strength of the C-P bond decreases with increasing strength of the N-P Lewis acid-Lewis base interaction. 

Relative bond strengths in hexacoordinated phosphorus compounds. In A, the N-P bond is 1.980Å long and the C-P is 1.833Å long, and in B, the N-P bond increases to 2.013Å as the C-P bond decreases to 1.814Å.

Pentacoordinated silicon

This trend is also generally true of pentacoordinated main-group elements with one or more lone-pair-containing ligand, including the oxygen-pentacoordinated silicon examples shown below. 

Relative bond strengths in pentacoordinated silicon compounds. In A, the Si-O bond length is 1.749Å and the Si-I bond length is 3.734Å; in B, the Si-O bond lengthens to 1.800Å and the Si-Br bond shortens to 3.122Å, and in C, the Si-O bond is the longest at 1.954Å and the Si-Cl bond the shortest at 2.307A.

 

The Si-halogen bonds range from close to the expected van der Waals value in A (a weak bond) almost to the expected covalent single bond value in C (a strong bond).

Reactivity

Silicon

Observed third-order reaction rate constants
for hydrolysis (displacement of chloride from silicon)

Chlorosilane	Nucleophile	kobs (M−2s−1) at 20 °C in anisole
Ph3SiCl	HMPT	1200
Ph3SiCl	DMSO	50
Ph3SiCl	DMF	6
MePh2SiCl	HMPT	2000
MePh2SiCl	DMSO	360
MePh2SiCl	DMF	80
Me(1-Np)PhSiCl	HMPT	3500
Me(1-Np)PhSiCl	DMSO	180
Me(1-Np)PhSiCl	DMF	40
(1-Np)Ph(vinyl)SiCl	HMPT	2200
(1-Np)Ph(vinyl)SiCl	DMSO	90
(1-Np)(m-CF3Ph)HSiCl	DMSO	1800
(1-Np)(m-CF3Ph)HSiCl	DMF	300

Corriu and coworkers performed early work characterizing reactions thought to proceed through a hypervalent transition state. Measurements of the reaction rates of hydrolysis of tetravalent chlorosilanes incubated with catalytic amounts of water returned a rate that is first order in chlorosilane and second order in water. This indicated that two water molecules interacted with the silane during hydrolysis and from this a binucleophilic reaction mechanism was proposed. Corriu and coworkers then measured the rates of hydrolysis in the presence of nucleophilic catalyst HMPT, DMSO or DMF. It was shown that the rate of hydrolysis was again first order in chlorosilane, first order in catalyst and now first order in water. Appropriately, the rates of hydrolysis also exhibited a dependence on the magnitude of charge on the oxygen of the nucleophile. 

Taken together this led the group to propose a reaction mechanism in which there is a pre-rate determining nucleophilic attack of the tetracoordinated silane by the nucleophile (or water) in which a hypervalent pentacoordinated silane is formed. This is followed by a nucleophilic attack of the intermediate by water in a rate determining step leading to hexacoordinated species that quickly decomposes giving the hydroxysilane.

Silane hydrolysis was further investigated by Holmes and coworkers in which tetracoordinated Mes₂SiF₂ (Mes = mesityl) and pentacoordinated Mes₂SiF₃⁻ were reacted with two equivalents of water. Following twenty-four hours, almost no hydrolysis of the tetracoordinated silane was observed, while the pentacoordinated silane was completely hydrolyzed after fifteen minutes. Additionally, X-ray diffraction data collected for the tetraethylammonium salts of the fluorosilanes showed the formation of hydrogen bisilonate lattice supporting a hexacoordinated intermediate from which HF₂⁻ is quickly displaced leading to the hydroxylated product. This reaction and crystallographic data support the mechanism proposed by Corriu et al.

 

Mechanism of silane hydrolysis and structure of the hydrogen bisilonate lattice

 

The apparent increased reactivity of hypervalent molecules, contrasted with tetravalent analogues, has also been observed for Grignard reactions. The Corriu group measured Grignard reaction half-times by NMR for related 18-crown-6 potassium salts of a variety of tetra- and pentacoordinated fluorosilanes in the presence of catalytic amounts of nucleophile.

Though the half reaction method is imprecise, the magnitudinal differences in reactions rates allowed for a proposed reaction scheme wherein, a pre-rate determining attack of the tetravalent silane by the nucleophile results in an equilibrium between the neutral tetracoordinated species and the anionic pentavalent compound. This is followed by nucleophilic coordination by two Grignard reagents as normally seen, forming a hexacoordinated transition state and yielding the expected product.

Grignard reaction mechanism for tetracoordinate silanes and the analogous hypervalent pentacoordinated silanes

 

The mechanistic implications of this are extended to a hexacoordinated silicon species that is thought to be active as a transition state in some reactions. The reaction of allyl- or crotyl-trifluorosilanes with aldehydes and ketones only precedes with fluoride activation to give a pentacoordinated silicon. This intermediate then acts as a Lewis acid to coordinate with the carbonyl oxygen atom. The further weakening of the silicon–carbon bond as the silicon becomes hexacoordinate helps drive this reaction.

Phosphorus

Similar reactivity has also been observed for other hypervalent structures such as the miscellany of phosphorus compounds, for which hexacoordinated transition states have been proposed. Hydrolysis of phosphoranes and oxyphosphoranes have been studied  and shown to be second order in water. Bel'skii et al.. have proposed a prerate determining nucleophilic attack by water resulting in an equilibrium between the penta- and hexacoordinated phosphorus species, which is followed by a proton transfer involving the second water molecule in a rate determining ring-opening step, leading to the hydroxlyated product. 

Mechanism of the hydrolysis of pentacoordinated phosphorus

 

Alcoholysis of pentacoordinated phosphorus compounds, such as trimethoxyphospholene with benzyl alcohol, have also been postulated to occur through a similar octahedral transition state, as in hydrolysis, however without ring opening.

Mechanism of the base catalyzed alcoholysis of pentacoordinated phosphorus

 

It can be understood from these experiments that the increased reactivity observed for hypervalent molecules, contrasted with analogous nonhypervalent compounds, can be attributed to the congruence of these species to the hypercoordinated activated states normally formed during the course of the reaction.

Ab initio calculations

The enhanced reactivity at pentacoordinated silicon is not fully understood. Corriu and coworkers suggested that greater electropositive character at the pentavalent silicon atom may be responsible for its increased reactivity. Preliminary ab initio calculations supported this hypothesis to some degree, but used a small basis set.

A software program for ab initio calculations, Gaussian 86, was used by Dieters and coworkers to compare tetracoordinated silicon and phosphorus to their pentacoordinate analogues. This ab initio approach is used as a supplement to determine why reactivity improves in nucleophilic reactions with pentacoordinated compounds. For silicon, the 6-31+G* basis set was used because of its pentacoordinated anionic character and for phosphorus, the 6-31G* basis set was used.

Pentacoordinated compounds should theoretically be less electrophilic than tetracoordinated analogues due to steric hindrance and greater electron density from the ligands, yet experimentally show greater reactivity with nucleophiles than their tetracoordinated analogues. Advanced ab initio calculations were performed on series of tetracoordinated and pentacoordinated species to further understand this reactivity phenomenon. Each series varied by degree of fluorination. Bond lengths and charge densities are shown as functions of how many hydride ligands are on the central atoms. For every new hydride, there is one less fluoride.

For silicon and phosphorus bond lengths, charge densities, and Mulliken bond overlap, populations were calculated for tetra and pentacoordinated species by this ab initio approach. Addition of a fluoride ion to tetracoordinated silicon shows an overall average increase of 0.1 electron charge, which is considered insignificant. In general, bond lengths in trigonal bipyramidal pentacoordinate species are longer than those in tetracoordinate analogues. Si-F bonds and Si-H bonds both increase in length upon pentacoordination and related effects are seen in phosphorus species, but to a lesser degree. The reason for the greater magnitude in bond length change for silicon species over phosphorus species is the increased effective nuclear charge at phosphorus. Therefore, silicon is concluded to be more loosely bound to its ligands.

Effects of fluorine substitution on positive charge density:

 

Comparison of Charge Densities with Degree of Fluorination for Tetra and Pentacoordinated Silicon

 

In addition Dieters and coworkers show an inverse correlation between bond length and bond overlap for all series. Pentacoordinated species are concluded to be more reactive because of their looser bonds as trigonal-bipyramidal structures.

Calculated bond length and bond overlap with degree of fluorination:

 

Comparison of Bond Lengths with Degree of Fluorination for Tetra and Pentacoordinated Silicon

 

Comparison of Bond Lengths with Degree of Fluorination for Tetra and Pentacoordinated Phosphorus

 

By calculating the energies for the addition and removal of a fluoride ion in various silicon and phosphorus species, several trends were found. In particular, the tetracoordinated species have much higher energy requirements for ligand removal than do pentacoordinated species. Further, silicon species have lower energy requirements for ligand removal than do phosphorus species, which is an indication of weaker bonds in silicon.