Magnetic Behaviour of vanadium hexacarbonyl

Bernier, J.C.; Kahn, Olivier

doi:10.1016/0009-2614(73)80394-x

Cited by 29 publications

(14 citation statements)

References 8 publications

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“…Indeed, V(CO) 6 was reported over 30 years ago and remains unique among this class of compounds because it is a stable radical and its derivatives were characterized long before metal-centered radicals were recognized as possibly being common and of general interest. Furthermore, even now, V(CO) 6 is the only simple binary metal carbonyl complex to be isolated as a radical monomer which is thermally stable to dimerization, and its electronic structure has been the subject of intense study. − V(CO) 6 readily undergoes carbonyl substitution with neutral, soft ligands (L) such as phosphines, forming 17-electron monomers of the general formula V(CO) 4 - n L n ( n = 1−4) . In general, the substituted carbonyl complexes are more thermally stable than is V(CO) 6 , and many have been isolated at room temperature.…”

mentioning

confidence: 99%

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)₄(Ph₂PCH₂CH₂PPh₂)

Koeslag¹,

Baird²,

Lovelace³

et al. 1996

Organometallics

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The novel 17-electron compound Ta(CO)4dppe (dppe = Ph2PCH2CH2PPh2) is formed via hydride hydrogen atom abstraction from TaH(CO)4dppe by the tris(p-tert-butylphenyl)methyl radical. The compound exists in solution as an equilibrium mixture of monomer (the dominant species) and carbonyl-bridged dimer [Ta(CO)4dppe]2 but solely as the latter in the solid state. It is very labile but was characterized electrochemically, IR, Raman, and 1H and 31P{1H} NMR spectroscopically, and chemically. Typical of metal-centered radicals, Ta(CO)4dppe abstracts halogen atoms from organic halides RX to give the halotantalum compounds TaX(CO)4dppe and, in some cases, TaR(CO)4dppe. Cyclic voltammetry experiments show that the oxidation of [Ta(CO)4(dppe)]- in CH2Cl2/0.1 M [Bu4N][PF6] is a one-electron process, irreversible at scan rates below 50 V/s. The formal potential of [Ta(CO)4(dppe)]0/- is estimated as −1.2 V vs ferrocene. The reduced lifetime of the radical is ascribed to reactions with the ionic medium, the main electrochemical oxidation products being TaH(CO)4(dppe) and TaCl(CO)2(dppe)2.

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mentioning

confidence: 99%

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)₄(Ph₂PCH₂CH₂PPh₂)

Koeslag¹,

Baird²,

Lovelace³

et al. 1996

Organometallics

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“…Later, however, this anomalous magnetic behavior was reinterpreted in terms of the vibronic coupling model of Van Vleck-Kotani and exchange magnetic interaction between two magnetic centers [41]. Our DFT studies [15] on V 2 (CO) 12 suggest instability with respect to dissociation into mononuclear V(CO) 6 fragments in contrast to the behavior of Mn 2 (CO) 10 and Co 2 (CO) 8 .…”

Section: Theoretical Methodsmentioning

confidence: 78%

The oxophilicity of vanadium in unsaturated homoleptic binuclear vanadium carbonyl structures

King

Schaefer

Liu

et al. 2008

Journal of Organometallic Chemistry

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“…Previous studies 56 on the WBIs of metal carbonyls including Fe 2 (CO) 9 and Fe 3 (CO) 12 have demonstrated that the WBIs of transition metal−metal bonds are relatively low compared with the formal bond orders. This is consistent with our observations on the WBIs of the Ti−Ti bonds in the Ti(CO) n derivatives.…”

Section: Resultsmentioning

confidence: 98%

“…However, these carbonyl dissociation energies of Ti 2 (CO) n (n = 12, 11) are significantly smaller than those predicted for mononuclear titanium carbonyls Ti(CO) n (n = 7, 6, 5). 15 Nevertheless, the larger CO dissociation energy of 21.4 (B3LYP) or 24.8 kcal/mol (BP86) from Ti 2 (CO) 10 to Ti 2 (CO) 9 (Table 2) 6 ]. 16 The thermochemistry of the dissociation of Ti 2 (CO) n into mononuclear fragments was also investigated ( Table 2).…”

Section: Resultsmentioning

confidence: 99%

“…These include extensive series of Cp 2 TiX 2 derivatives in which the titanium has only a 16-electron configuration. 21,22 For the binuclear binary titanium carbonyls Ti 2 (CO) n in which the titanium atoms have only 16-electron configurations, Ti 2 (CO) 11 would have a formal Ti−Ti single bond, Ti 2 (CO) 10 would have a formal TiTi double bond, Ti 2 (CO) 9 would have a formal TiTi triple bond, and so forth. However, no examples of stable titanium carbonyl derivatives or related compounds are known with any type of Ti−Ti bonds.…”

Section: Introductionmentioning

confidence: 99%

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New Titanium Carbonyls: Ti₂(CO)₁₀, Ti₂(CO)₁₁, and Ti₂(CO)₁₂

et al. 2015

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Structural and energetic features of the binuclear titanium carbonyls Ti2(CO)n (n = 12, 11, 10) have been examined using density functional theory. The lowest-energy Ti2(CO)12 structure is a singlet structure consisting of two Ti(CO)6 units linked by Ti═Ti double bonds of lengths 3.0-3.2 Å. A similar slightly higher energy triplet Ti2(CO)12 structure is found with longer Ti-Ti bonds (3.37-3.62 Å), considered to be formal single bonds. The energy required for the dissociation of Ti2(CO)12 into two Ti(CO)6 fragments is 18.5 ± 2 kcal/mol higher than the energy required for the dissociation of V2(CO)12 into two V(CO)6 fragments. For the unsaturated Ti2(CO)11 system, the lowest-energy structures contain a four-electron-donor bridging η(2)-μ-CO group and 10 terminal CO groups with formal Ti═Ti double bonds in the singlet structures and formal Ti-Ti single bonds in the triplet structures. Similarly, the most favored geometries for the more highly unsaturated Ti2(CO)10 contain two four-electron-donor bridging η(2)-μ-CO groups with formal Ti═Ti double bonds for the singlet structures and formal Ti-Ti single bonds for the triplet structures. Higher-energy triplet Ti2(CO)10 structures are found with two or three two-electron-donor semibridging CO groups and formal Ti≡Ti triple bonds of length 2.7-2.8 Å.

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Magnetic Behaviour of vanadium hexacarbonyl

Cited by 29 publications

References 8 publications

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)₄(Ph₂PCH₂CH₂PPh₂)

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)₄(Ph₂PCH₂CH₂PPh₂)

The oxophilicity of vanadium in unsaturated homoleptic binuclear vanadium carbonyl structures

New Titanium Carbonyls: Ti₂(CO)₁₀, Ti₂(CO)₁₁, and Ti₂(CO)₁₂

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Magnetic Behaviour of vanadium hexacarbonyl

Cited by 29 publications

References 8 publications

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)4(Ph2PCH2CH2PPh2)

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)4(Ph2PCH2CH2PPh2)

The oxophilicity of vanadium in unsaturated homoleptic binuclear vanadium carbonyl structures

New Titanium Carbonyls: Ti2(CO)10, Ti2(CO)11, and Ti2(CO)12

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Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)₄(Ph₂PCH₂CH₂PPh₂)

Synthesis and Properties of the 17-Electron, Tantalum-Centered Radical Ta(CO)₄(Ph₂PCH₂CH₂PPh₂)

New Titanium Carbonyls: Ti₂(CO)₁₀, Ti₂(CO)₁₁, and Ti₂(CO)₁₂