The Hydrido‐Transition Metal Cluster Complexes

Humphries, Adrian; Kaesz, H. D.

doi:10.1002/9780470166260.ch3

Cited by 73 publications

(5 citation statements)

References 182 publications

(148 reference statements)

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“…Although there are not many examples, there is clear evidence that electronic unsaturation can produce significant deshielding effects on bridging hydrido ligands. For example, the hydride resonances of the unsaturated complexes Re 4 (CO) 12 (μ 3 -H) 4 and Os 3 (CO) 10 (μ-H) 2 are much less shielded than those of related saturated cluster complexes . The Re−Re bond distance in 4 , Re1−Re2 = 3.1083(3) Å, is slightly shorter than the Re−Re bond distances in 1 and 2 .…”

Section: Resultsmentioning

confidence: 94%

Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBu^t₃ Ligand

2007

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Five new complexes were obtained from the reaction of Re3(CO)12(μ-H)3 with PBut 3. These are Re2(CO)8(μ-PBut 2)(μ-H), 1, Re2(CO)7(μ-PBut 2)(PBut 2H)(μ-H), 2, HRe(CO)4(PBut 3), 3, Re2(CO)6(PBut 3)(μ-PBut 2)(μ-H), 4, and Re2(CO)5(PBut 3)(PBut 2H)(μ-PBut 2O)(μ-H), 5. Compounds 4 and 5 are electronically unsaturated by the amount of two electrons; namely, one of the metal atoms has an 18-electron configuration and the other metal atom has a 16-electron configuration. Compound 4 adds CO and the nitriles MeCN and PhCN, reversibly, to form the electronically saturated 1:1 adducts Re2(CO)7(PBut 3)(μ-PBut 2)(μ-H), 6, Re2(CO)6(NCMe)(PBut 3)(μ-PBut 2)(μ-H), 7, and Re2(CO)6(NCPh)(PBut 3)(μ-PBut 2)(μ-H), 8, respectively. 13CO labeling studies have shown that the CO ligand that is added to 4 to form 6 is added at the electronically saturated metal atom and one of the originally coordinated CO ligands is shifted to the unsaturated metal atom. Compound 5 also adds 1 equiv of CO to form the complex Re2(CO)6(PBut 3)(PBut 2H)(μ-PBut 2O)(μ-H), 9.13CO labeling studies have shown that the added CO ligand was added to the unsaturated metal atom in this case. All of the new compounds were characterized structurally by single-crystal X-ray diffraction analyses.

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Section: Resultsmentioning

confidence: 94%

Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBu^t₃ Ligand

2007

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“…The molecular structure shows that the benzoyl formate ligand occupies two axial positions on adjacent osmium atoms. The Os(1A)-Os(2A) [2.9297(5) Å ] edge is longer than the Os(1A)-Os(3A) [2.8562(4) Å ] and Os(2A)-Os(3A) [2.8708(5) Å ] edges, which is a common feature of hydride-bridged Os-Os edges [10]. The Os(1A)-C(12A) [1.867(6) Å ] and Os(2A)-C(22A) [1.864(6) Å ] bonds are shorter than the Os(3A)-C(32A) [1.964(7) Å ] bond.…”

Section: Studies On the Incorporation Of Clusters Into Tamoxifenmentioning

confidence: 99%

“…1. For the synthesis of triosmium-carboxylate clusters, the parent triosmium carbonyl cluster Os 3 (CO) 12 , 1a, is of limited utility as it is rather inert; often an activated derivative such as Os 3 (CO) 10 (NCMe), 2a, Os 3 (CO) 10 (NCMe) 2 , 2b, or Os 3 (CO) 10 (l-H)(l-OH), 3, is employed instead. Triosmium-carboxylate clusters can be conveniently prepared by the reaction of 3 with the appropriate carboxylic acid in the presence of HBF 4 AE OEt 2 as an acid catalyst [8].…”

Section: Studies On the Incorporation Of Clusters Into Tamoxifenmentioning

confidence: 99%

Organometallic cluster analogues of tamoxifen: Synthesis and biochemical assay

Chan¹,

Leong²,

Jaouen³

et al. 2006

Journal of Organometallic Chemistry

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“…The two species are effectively isolobal and both contain only one valence electron. H and the Au(PPh 3 ) group are well-known to bridge metal–metal bonds effectively in polynuclear metal complexes. , There are a number of hydride-bridged metal carbonyl cluster complexes, such as Re 2 (CO) 8 (μ-H) 2 , A , Os 3 (CO) 10 (μ-H) 2 , B , Re 4 (CO) 12 (μ-H) 4 , C , and higher nuclearity cluster complexes, such as Pt 2 Re 3 (CO) 9 (P- t -Bu 3 ) 3 (μ-H) 6 , and [Ru 3 (CO) 8 (μ 3 -CMe)(μ-H) 2 (μ 3 -H)] 2 , that have attracted interest because they are formally electronically unsaturated. Unsaturated metal cluster complexes are of interest because they exhibit higher reactivity than their electronically saturated counterparts. − A few unsaturated triosmium carbonyl cluster complexes containing the bridging Au(PR 3 ) group(s) have also been prepared (e.g., Os 3 (CO) 10 (μ-AuPEt 3 ) 2 , Os 3 (CO) 10 (μ-AuPPh 3 )(μ-H), and Os 3 (CO) 10 (μ-AuPPh 3 )(μ-Ph)) that are related to Os 3 (CO) 10 (μ-H) 2 .…”

Section: Introductionmentioning

confidence: 99%

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

2013

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The compounds Re2(CO)8(μ-AuPPh3)2, 1, a dimer of Re(CO)4(μ-AuPPh3), and ax,ax-Re2(CO)8(PPh3)2 were obtained from UV–vis radiation-induced decarbonylation of the compound Re(CO)5[Au(PPh3)]. Compound 1 contains two rhenium atoms bridged by two AuPPh3 groups. The complex has 32 valence electrons and is formally unsaturated by the amount of two electrons. The Re–Re bond distance in 1 is unusually short (Re–Re = 2.9070(3) Å), as found by a single-crystal structural analysis. The nature of the metal–metal bonding in 1 was investigated by DFT computational analyses, which have provided evidence not only for σ-bonding but also significant complementary π-bonding directly between the two rhenium atoms. The electronic structure of Re2(CO)8(μ-H)2, 2, was similarly analyzed and is compared with that of 1. Compound 1 is intensely colored due to low-energy, metal-based electronic transitions between the HOMO and HOMO-2 and the LUMO. Compound 1 reacts with I2 to yield Re2(CO)8(μ-AuPPh3)(μ-I), 3, and the known compound Re2(CO)8(μ-I)2, 4, by substitution of the bridging AuPPh3 groups with bridging iodide ligands. Compound 3 is electronically saturated, 34 valence electrons, and contains a formal Re–Re single bond: Re–Re = 3.2067(5) Å. Compound 3 was also in a high yield (83%) from the reaction of Re2(CO)8(μ-H)(μ-CHCHC4H9) with Au(PPh3)I. The Re–Re bonding in compounds 3, 4, and Re2(CO)10 was also analyzed computationally, and this bonding was compared with their bonding in 1 and 2.

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The Hydrido‐Transition Metal Cluster Complexes

Cited by 73 publications

References 182 publications

Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBu^t₃ Ligand

Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBu^t₃ Ligand

Organometallic cluster analogues of tamoxifen: Synthesis and biochemical assay

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

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The Hydrido‐Transition Metal Cluster Complexes

Cited by 73 publications

References 182 publications

Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBut3 Ligand

Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBut3 Ligand

Organometallic cluster analogues of tamoxifen: Synthesis and biochemical assay

Studies of the Structures and Bonding of Gold-Bridged Dirhenium Carbonyl Cluster Complexes

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Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBu^t₃ Ligand

Studies of Ligand Additions to Coordinatively Unsaturated Dirhenium Complexes Containing the Bulky PBu^t₃ Ligand