Pentacarbonyl[methyl(<i>n</i>-propylsulfanyl)carbene]chromium(0)

Esterhuysen, Catharine; Even, J.; Esterhuysen, Matthias W.; Horvath, Ulrike E. I.; Stander, Elzet; Raubenheimer, Helgard G.

doi:10.1107/s1600536806022902

Cited by 2 publications

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“…This explains the bias of thio-substituted carbenes for the syn -isomers. These computational findings fully match the crystallographical data for the few reported X-ray structures of Fischer thiocarbene complexes …”

Section: Resultssupporting

confidence: 85%

Steric versus Electronic Effects in the Structure of Heteroatom (S and O)-Substituted Free and Metal (Cr and W)-Complexed Carbenes

et al. 2007

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DFT computational energies for free alkoxy-and thio-substitued free carbenes correlate with experimental steric data (Taft parameters) showing the importance of the steric volume at the expense of the electronic interaction in determining the conformation of free carbenes 1-14. The shorter C-O bond distances in the alkoxy derivatives render alkoxycarbene more sensitive to steric effects than thiocarbenes. This strong dependence of the conformation with the steric hindrance is not applicable to metal-complexed carbenes. Thio-substituted carbene complexes exist exclusively as syn-isomers due to the combination of an interaction of the sulfur lone pair with two CO ligands and the steric repulsion with the "CO-wall". The stronger C carbene -S bond compared to C carbene -O is responsible for the increased syn-anti rotation barrier observed for the alkylthio-substituted metal carbene complexes compared to their oxygen analogues. The differences of polarity between syn-and anti-isomers of alkylthio-substituted metal carbene complexes explain also the increment of the isomerization barrier with the polarity of the solvent. The effect of the substituent attached to the carbene carbon is not decisive in the conformation of these compounds.

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Section: Resultssupporting

confidence: 85%

Steric versus Electronic Effects in the Structure of Heteroatom (S and O)-Substituted Free and Metal (Cr and W)-Complexed Carbenes

et al. 2007

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Aurolysis of α-C-deprotonated group 6 aminocarbene and thiocarbene complexes with Ph₃PAu⁺

et al. 2006

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Deprotonated Fischer-type aminocarbene complexes, (CO)5M=C(NR2)CH3 (M = Cr or W; R = Me or propyl), react with Ph3PAu+ by metal group substitution - (CO)5M for Ph3PAu+--and attachment of the extricated M(CO)5 to the deprotonated methyl group. (The products may also be seen as aminovinylgold compounds coordinated to M(CO)5 moieties.) DFT calculations at the B3LYP level of theory using model compounds indicate a clear preference of the gold unit for central C to terminal coordination in the ligand [NMe2CCH2]-, whereas the Cr(CO)5 has a 7 kcal mol(-1) preference for C(vinyl) coordination compared to N-coordination. In related thiocarbenes, the sulfur donor atom should be the preferred point of attachment for the metal carbonyl unit. The latter prediction is borne out in practice, and in the three products isolated, including Ph3PAu{C(=CH2)SPh}Cr(CO)5 in a mixed crystal with [Ph3PAuSPh]Cr(CO)5, precisely this coordination mode is present. The latter component of the mixed crystal has also been prepared independently of the vinyl one.

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Pentacarbonyl[methyl(n-propylsulfanyl)carbene]chromium(0)

Abstract: The title compound, [Cr(C5H10S)(CO)5], comprises a methyl(n-propylsulfanyl)carbene ligand coordinated to a pentacarbonylchromium fragment, with the Cr atom in an octahedral coordination.

Cited by 2 publications

References 6 publications

Steric versus Electronic Effects in the Structure of Heteroatom (S and O)-Substituted Free and Metal (Cr and W)-Complexed Carbenes

Steric versus Electronic Effects in the Structure of Heteroatom (S and O)-Substituted Free and Metal (Cr and W)-Complexed Carbenes

Aurolysis of α-C-deprotonated group 6 aminocarbene and thiocarbene complexes with Ph₃PAu⁺

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Pentacarbonyl[methyl(n-propylsulfanyl)carbene]chromium(0)

Abstract: The title compound, [Cr(C5H10S)(CO)5], comprises a methyl(n-propylsulfanyl)carbene ligand coordinated to a pentacarbonylchromium fragment, with the Cr atom in an octahedral coordination.

Cited by 2 publications

References 6 publications

Steric versus Electronic Effects in the Structure of Heteroatom (S and O)-Substituted Free and Metal (Cr and W)-Complexed Carbenes

Steric versus Electronic Effects in the Structure of Heteroatom (S and O)-Substituted Free and Metal (Cr and W)-Complexed Carbenes

Aurolysis of α-C-deprotonated group 6 aminocarbene and thiocarbene complexes with Ph3PAu+

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Aurolysis of α-C-deprotonated group 6 aminocarbene and thiocarbene complexes with Ph₃PAu⁺