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Papers by Carl Hollandsworth
Acta Crystallographica Section E-structure Reports Online, 2005
ABSTRACT
Journal of Organometallic Chemistry, 2006
Thiolysis of W 2 Cp 2 (NMe 2 ) 4 and W 2 COT(NMe 2 ) 4 with excess Bu t SH leads to cleavage of t... more Thiolysis of W 2 Cp 2 (NMe 2 ) 4 and W 2 COT(NMe 2 ) 4 with excess Bu t SH leads to cleavage of the respective carbocyclic rings from the ditungsten center and formation of the compound anti-1,2-W 2 (SBu t ) 2 (NMe 2 ) 4 which was characterized via a single-crystal X-ray diffraction study. This product was found to be isostructural with its dimolybdenum analogue. The compound is a prototypical ethane-like dimer having a W"W bond distance of 2.3011(3) Å and thiolate ligands in an anti configuration about the W"W bond. The thiolysis reactions for both dimethylamide precursors are contrasted with the results of their respective alcoholysis reactions.
Cheminform, 2007
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Journal of Cluster Science, 2005
ABSTRACT
Polyhedron, 2006
Dedicated to Professor M.B. Hursthouse on the occasion of his 65 birthday.
Journal of The Chemical Society-dalton Transactions, 2002
ABSTRACT
Inorganic Chemistry Communications, 2006
ABSTRACT
Journal of Organometallic Chemistry, 2003
... selected. Journal of Organometallic Chemistry Volume 684, Issues 1-2, 1 November 2003, Pages ... more ... selected. Journal of Organometallic Chemistry Volume 684, Issues 1-2, 1 November 2003, Pages 269-276 Metal-Carbon Multiple Bonds and Related Organometallics Dedicated to Professor EO Fischer on his 85th Birthday. doi ...
The coordination chemistry of the X3M≡MX3 “ethane-like dimers” of molybdenum and tungsten is rich... more The coordination chemistry of the X3M≡MX3 “ethane-like dimers” of molybdenum and tungsten is rich and varied. Though the chemistry of the (Mo≡Mo)6+ and (W≡W)6+ units are very similar, there are significant differences. The ditungsten center is notably more readily oxidized and this leads to a much more extensive organometallic chemistry of small, unsaturated organic molecules. Many of these reactions lead to the reduction and cleavage of C—X multiple bonds. In contrast, reductive eliminations occur more readily from the Mo2 6+ center to give Mo2 4+ compounds having MM quadruple bonds. Furthermore, the ditungsten compounds are much more labile towards forming clusters. The organometallic chemistry of the M2(OR)6 compounds bears a superficial resemblance to that of the Cp2M2(CO)4 compounds, though it is evident that despite the difference in formal oxidation states, the M2(OR)6 compounds are more reactive as electron reservoirs.
Organometallics, 2006
ABSTRACT A series of new bimetallic cluster compounds, Cp2M2(CO)4[M‘(PBut3)]2 [M = Mo, M‘ = Pt (9... more ABSTRACT A series of new bimetallic cluster compounds, Cp2M2(CO)4[M‘(PBut3)]2 [M = Mo, M‘ = Pt (9); M = Mo, M‘ = Pd (10); M = W, M‘ = Pt (11); M = W, M‘ = Pd (12)], have been synthesized from reactions of [CpM(CO)3]2 (M = Mo, W) with an excess of M‘(PBut3)2 (M‘ = Pt, Pd) at various temperatures. Each compound was fully characterized by IR, 1H and 31P NMR, and single-crystal X-ray diffraction analyses. The metal atoms in the structure of 9 are arranged in a butterfly configuration, while the metal atoms of 10−12 adopt a tetrahedral geometry. Compounds 9 and 12 contain two edge-bridging and two triply bridging carbonyl ligands, 10 contains four triply bridging carbonyl ligands, and 11 contains two terminal and two edge-bridging carbonyl ligands. Each of the products is electron-deficient and the M−M bonds, M = Mo and W, are short, Mo−Mo = 2.6535(4) Å in 9 and 2.6362(4) Å in 10, W−W = 2.6168(9) Å in 11 and 2.6320(7) Å in 12, which is indicative of some localized multibond character between these metal atoms within the cluster framework. The nature of the bonding within the clusters was explored with DFT calculations (ADF 2004.01, PW91) for the title compounds in C2 symmetry as well as for a hypothetical, two-electron-reduced [Cp2Mo2Pd2(CO)4(PBut3)2]2- species.
Acta Crystallographica Section E-structure Reports Online, 2005
ABSTRACT
Journal of Organometallic Chemistry, 2006
Thiolysis of W 2 Cp 2 (NMe 2 ) 4 and W 2 COT(NMe 2 ) 4 with excess Bu t SH leads to cleavage of t... more Thiolysis of W 2 Cp 2 (NMe 2 ) 4 and W 2 COT(NMe 2 ) 4 with excess Bu t SH leads to cleavage of the respective carbocyclic rings from the ditungsten center and formation of the compound anti-1,2-W 2 (SBu t ) 2 (NMe 2 ) 4 which was characterized via a single-crystal X-ray diffraction study. This product was found to be isostructural with its dimolybdenum analogue. The compound is a prototypical ethane-like dimer having a W"W bond distance of 2.3011(3) Å and thiolate ligands in an anti configuration about the W"W bond. The thiolysis reactions for both dimethylamide precursors are contrasted with the results of their respective alcoholysis reactions.
Cheminform, 2007
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Journal of Cluster Science, 2005
ABSTRACT
Polyhedron, 2006
Dedicated to Professor M.B. Hursthouse on the occasion of his 65 birthday.
Journal of The Chemical Society-dalton Transactions, 2002
ABSTRACT
Inorganic Chemistry Communications, 2006
ABSTRACT
Journal of Organometallic Chemistry, 2003
... selected. Journal of Organometallic Chemistry Volume 684, Issues 1-2, 1 November 2003, Pages ... more ... selected. Journal of Organometallic Chemistry Volume 684, Issues 1-2, 1 November 2003, Pages 269-276 Metal-Carbon Multiple Bonds and Related Organometallics Dedicated to Professor EO Fischer on his 85th Birthday. doi ...
The coordination chemistry of the X3M≡MX3 “ethane-like dimers” of molybdenum and tungsten is rich... more The coordination chemistry of the X3M≡MX3 “ethane-like dimers” of molybdenum and tungsten is rich and varied. Though the chemistry of the (Mo≡Mo)6+ and (W≡W)6+ units are very similar, there are significant differences. The ditungsten center is notably more readily oxidized and this leads to a much more extensive organometallic chemistry of small, unsaturated organic molecules. Many of these reactions lead to the reduction and cleavage of C—X multiple bonds. In contrast, reductive eliminations occur more readily from the Mo2 6+ center to give Mo2 4+ compounds having MM quadruple bonds. Furthermore, the ditungsten compounds are much more labile towards forming clusters. The organometallic chemistry of the M2(OR)6 compounds bears a superficial resemblance to that of the Cp2M2(CO)4 compounds, though it is evident that despite the difference in formal oxidation states, the M2(OR)6 compounds are more reactive as electron reservoirs.
Organometallics, 2006
ABSTRACT A series of new bimetallic cluster compounds, Cp2M2(CO)4[M‘(PBut3)]2 [M = Mo, M‘ = Pt (9... more ABSTRACT A series of new bimetallic cluster compounds, Cp2M2(CO)4[M‘(PBut3)]2 [M = Mo, M‘ = Pt (9); M = Mo, M‘ = Pd (10); M = W, M‘ = Pt (11); M = W, M‘ = Pd (12)], have been synthesized from reactions of [CpM(CO)3]2 (M = Mo, W) with an excess of M‘(PBut3)2 (M‘ = Pt, Pd) at various temperatures. Each compound was fully characterized by IR, 1H and 31P NMR, and single-crystal X-ray diffraction analyses. The metal atoms in the structure of 9 are arranged in a butterfly configuration, while the metal atoms of 10−12 adopt a tetrahedral geometry. Compounds 9 and 12 contain two edge-bridging and two triply bridging carbonyl ligands, 10 contains four triply bridging carbonyl ligands, and 11 contains two terminal and two edge-bridging carbonyl ligands. Each of the products is electron-deficient and the M−M bonds, M = Mo and W, are short, Mo−Mo = 2.6535(4) Å in 9 and 2.6362(4) Å in 10, W−W = 2.6168(9) Å in 11 and 2.6320(7) Å in 12, which is indicative of some localized multibond character between these metal atoms within the cluster framework. The nature of the bonding within the clusters was explored with DFT calculations (ADF 2004.01, PW91) for the title compounds in C2 symmetry as well as for a hypothetical, two-electron-reduced [Cp2Mo2Pd2(CO)4(PBut3)2]2- species.