Mixed-valence dimolybdenum complexes containing hard oxo and soft carbonyl ligands: synthesis, structure, and electrochemistry of Mo2 (O)(CO)2 (μ-κ2 -S(CH2 )n S)2 (κ2 -diphosphine)

Dalton Transactions : an International Journal of Inorganic Chemistry
Mohd Rezaul HaqueShariff E Kabir

Abstract

Mixed-valence dimolybdenum complexes Mo2(O)(CO)2{μ-κ2-S(CH2)nS}2(κ2-Ph2P(CH2)mPPh2) (n = 2, 3; m = 1, 2) (1-4) have been synthesized from one-pot reactions of fac-Mo(CO)3(NCMe)3 and dithiols, HS(CH2)nSH, in the presence of diphosphines. The dimolybdenum framework is supported by two thiolate bridges, with one molybdenum carrying a terminal oxo ligand and the second two carbonyls. The dppm (m = 1) products exist as a pair of diastereomers differing in the relative orientation of the two carbonyls (cis and trans) at the Mo(CO)2(dppm) center, while dppe (m = 2) complexes are found solely as the trans isomers. Small amounts of Mo(CO){κ3-S(CH2CH2S)2}(κ2-dppe) (5) also result from the reaction using HS(CH2)2SH and dppe. The bonding in isomers of 1-4 has been computationally explored by DFT calculations, trans diastereomers being computed to be more stable than the corresponding pair of cis diastereomers for all. The calculations confirm the existence of Mo[triple bond, length as m-dash]O and Mo-Mo bond orders and suggest that the new dimeric compounds are best viewed as Mo(v)-Mo(i) mixed-valence systems. The electrochemical properties of 1 have been investigated by CV and show a reversible one-electron reduction associated with the M...Continue Reading

References

Sep 2, 2004·Journal of the American Chemical Society·Chao-Yi ChiangMarcetta Y Darensbourg
Dec 8, 2004·Archives of Biochemistry and Biophysics·Russ Hille
Jul 19, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Fritz E KühnWolfgang A Herrmann
May 20, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Maria João Romão
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May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Ganna LyashenkoNadia C Mösch-Zanetti
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Jul 3, 1998·Angewandte Chemie·Vincent E KaasjagerJan Reedijk

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

JIMP2
NaturalBond Orbital ( NBO )
Gaussian
Crystal Clear

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