Synthesis and structures of binuclear half-sandwich cobalt (III) ortho-carboranedithiolato complexes with silyl-bridged bis(cyclopentadienyl) ligands

Hou, Xiu‐Feng; Zhang, Pengcheng; Liu, Shu; Wang, Hui; Lin, Yue-Jiang; Jin, Guo‐Xin

doi:10.1016/j.jorganchem.2007.07.046

Cited by 12 publications

(5 citation statements)

References 32 publications

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“…In 4 two of the three cobalt atoms present a similar coordination sphere, with each metal bonded to two μ 3 -S atoms, one sulfur atom of the individual carborane dithiolato ligands and one Cp ligand, giving rise to a three-legged piano-stool geometry. The Co···Co distance of 3.316 Å between the two CpCo units is much longer than a typical Co−Co bond length in a range of 2.30−2.95 Å reported in literature. , The third cobalt atom has a coordination environment consisting of six sulfur atoms in a distorted octahedral geometry, being coordinated by four μ 3 -S atoms and two sulfur atoms from the two different carborane thiolato ligands. The Co···Co distances between each CpCo unit and the third cobalt atom are 2.919 and 2.927 Å, respectively.…”

Section: Resultsmentioning

confidence: 68%

“…Whereas the central cobalt atom, occupying a crystallographic inversion center, is coordinated by six ( n -BuS) − ligands in a distorted octahedral geometry. The Co···Co···Co angle is 180°, and the Co···Co distance is 2.955 Å, longer than 2.30−2.95 Å for a typical Co−Co bond. , Each cobalt has a charge of +3, thus the cation has a charge of −1. Such a cation is the first example, even though linear-type trinuclear cobalt species and sulfur-bridged trinuclear cobalt compounds have been previously reported. , Alkanethiolato ligand is still rarely utilized to design thiolate-bridged supramolecular structures …”

Section: Resultsmentioning

confidence: 99%

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Ligand-to-Metal Ratio Controlled Assembly of Cobalt Complexes Containing ortho-Carborane Thiolato and Butyl Thiolato Ligands

Jiang

et al. 2010

Inorg. Chem.

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Treatment of ortho-carborane, n-butyl lithium, sulfur, and CpCo(CO)I(2) with differing ratios led to four new compounds [(CpCoS(2)C(2)B(10)H(10))(CpCoSC(2)B(10)H(11))(SC(4)H(9))] (3), [(CpCo)(2)S(2)(S(2)C(2)B(10)H(10)) (SC(2)B(10)H(10))(SC(4)H(9))] (4), [(CpCo)(2)Co(SC(4)H(9))(6)](+)[Co(S(2)C(2)B(10)H(10))(2)](-) (5), and [(CpCo)(2)Co(SC(2)B(10)H(11))(SC(4)H(9))(5)](+)[Co(S(2)C(2)B(10)H(10))(2)](-) (6). Compound 3 contains a rhombic Co(2)(mu(2)-S)(2) core and can be considered as an adduct of the two 16e half-sandwich monomers CpCo(S(2)C(2)B(10)H(10)) (1) and CpCo(SC(4)H(9))(SC(2)B(10)H(11)). Compound 4 is a trinuclear complex containing a cuboidal [Co(3)(mu(3)-S)(2)(mu-S)(2)] core, and one cobalt atom is coordinated by six sulfur atoms in a distorted octahedral geometry. Compound 5 consists of a linear-type trinuclear cobalt(III) monocation bridged by six n-butyl thiolato units and a square-planar cobalt(III) monoanion [Co(S(2)C(2)B(10)H(10))(2)](-). However, in 6, one ortho-carborane monothiolato ligand [SC(2)B(10)H(11)](-) has replaced one n-butyl thiolato ligand in 5. This leads to a nonlinear arrangement of the three cobalt atoms in the cation and the nonplanar [Co(S(2)C(2)B(10)H(10))(2)](-) anion in 6. Interestingly, the treatment of the 16e half-sandwich CpCo(S(2)C(2)B(10)H(10)) (1) by [N(n-Bu)(4)]Br afforded the ionic compound 7, [N(n-Bu)(4)](+)[Co(S(2)C(2)B(10)H(10))(2)](-), containing a square-planar anion.

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Section: Resultsmentioning

confidence: 68%

Section: Resultsmentioning

confidence: 99%

Ligand-to-Metal Ratio Controlled Assembly of Cobalt Complexes Containing ortho-Carborane Thiolato and Butyl Thiolato Ligands

Jiang

et al. 2010

Inorg. Chem.

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“…Interestingly, the synthesis of its parent compound ( 1 ) by the same method was unsuccessful. However, it could be prepared by a modification of this method or by a totally different route…”

Section: Resultsmentioning

confidence: 99%

“…Photolyses were conducted with a 250 W high-pressure Hg lamp in an ice–water bath. The doubly bridged bis(cyclopentadiene) (C 5 H 4 (SiMe 2 )) 2 ( 1 ) was prepared by the literature method …”

Section: Methodsmentioning

confidence: 99%

“…To develop a deeper understanding of the migration behavior during reactions of doubly bridged bis(cyclopentadienes) with transition-metal complexes, in this paper we have turned our attention to the simple, symmetric doubly bridged ligand precursors (C 5 H 3 R(SiMe 2 )) 2 (R = H ( 1 ), t Bu ( 2 )) (Chart ) and explored their reactions with Mo(CO) 6 and Fe(CO) 5 in refluxing xylene. Although the reactions of 1 and [ 1 ] 2– anion with transition-metal carbonyls have been extensively studied, − none of them involved migration of the bridging SiMe 2 group under the respective conditions.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of Doubly SiMe₂-Bridged Bis(cyclopentadienyl) Complexes of Molybdenum and Iron Carbonyls: Competitive Ring-to-Metal Migrations of Hydrogen and SiMe₂

et al. 2012

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Reaction of the doubly bridged bis-(cyclopentadiene) (C 5 H 4 (SiMe 2 )) 2 (1) with Mo(CO) 6 in refluxing xylene gave the corresponding dinuclear molybdenum carbonyl complex [(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 ]Mo 2 (CO) 6 (3) and the desilylated product [(η 5 -C 5 H 4 ) 2 (SiMe 2 )]Mo 2 (CO) 6 ( 6), together with the singly SiMe 2 SiMe 2 -bridged dinuclear molybdenum product [(η 5 -C 5 H 4 ) 2 (SiMe 2 SiMe 2 )]Mo 2 (CO) 6 (5) and the novel complex [(SiMe 2 )(η 5 -C 5 H 4 )Mo(CO) 3 ] 2 (4) containing two Mo−Si bonds. This diversity of products is caused by similar ring-to-metal migrating abilities of the hydrogen and SiMe 2 groups and their competitive migration during the reactions. Reaction of the dihydride cis-[(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 ]-Mo 2 (CO) 6 (H) 2 (7c) in refluxing xylene also afforded the above products except 4, which suggests that 7c might be intermediate precursor to 3, 5, and 6. Similar treatment of substituted doubly bridged bis(cyclopentadiene) (C 5 H 3 t Bu(SiMe 2 )) 2 (2) with Mo(CO) 6 provided the corresponding derivatives (8−10) of the above products and the product [(η 5 -C 5 H 4 t Bu)Mo(CO) 3 ] 2 (11), in which both SiMe 2 groups are removed. Heating a mixture of 1 and Fe(CO) 5 in xylene yielded the normal dinuclear iron complex [(η 5 -C 5 H 3 ) 2 (SiMe 2 ) 2 ]Fe 2 (CO) 2 (μ-CO) 2 (12) and the desilylated product [(η 5 -C 5 H 4 ) 2 (SiMe 2 )]Fe 2 (CO) 2 (μ-CO) 2 ( 14), together with the novel complex (SiMe 2 )(η 5 -C 5 H 3 )(η 5 :η 1 -C 5 H 3 )[(SiMe 2 )-Fe(CO) 2 ][Fe(CO) 2 )] (13) containing one Fe−Si bond. However, similar treatment of 2 with Fe(CO) 5 provided only the corresponding dinuclear complex [(η 5 -C 5 H 2 t Bu) 2 (SiMe 2 ) 2 ]Fe 2 (CO) 4 (15), in which the Fe−Fe bond (2.8205(9) Å) is the longest among all dimeric Cp′ 2 Fe 2 (CO) 4 analogues. A plausible mechanism for the formation of the different types of products is proposed. Molecular structures of 4, 9c, 13, and 15 determined by X-ray diffraction are also presented.

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Icosahedral Carboranes

Grimes¹

2011

Carboranes

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Synthesis and structures of binuclear half-sandwich cobalt (III) ortho-carboranedithiolato complexes with silyl-bridged bis(cyclopentadienyl) ligands

Cited by 12 publications

References 32 publications

Ligand-to-Metal Ratio Controlled Assembly of Cobalt Complexes Containing ortho-Carborane Thiolato and Butyl Thiolato Ligands

Ligand-to-Metal Ratio Controlled Assembly of Cobalt Complexes Containing ortho-Carborane Thiolato and Butyl Thiolato Ligands

Reactions of Doubly SiMe₂-Bridged Bis(cyclopentadienyl) Complexes of Molybdenum and Iron Carbonyls: Competitive Ring-to-Metal Migrations of Hydrogen and SiMe₂

Icosahedral Carboranes

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Synthesis and structures of binuclear half-sandwich cobalt (III) ortho-carboranedithiolato complexes with silyl-bridged bis(cyclopentadienyl) ligands

Cited by 12 publications

References 32 publications

Ligand-to-Metal Ratio Controlled Assembly of Cobalt Complexes Containing ortho-Carborane Thiolato and Butyl Thiolato Ligands

Ligand-to-Metal Ratio Controlled Assembly of Cobalt Complexes Containing ortho-Carborane Thiolato and Butyl Thiolato Ligands

Reactions of Doubly SiMe2-Bridged Bis(cyclopentadienyl) Complexes of Molybdenum and Iron Carbonyls: Competitive Ring-to-Metal Migrations of Hydrogen and SiMe2

Icosahedral Carboranes

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Reactions of Doubly SiMe₂-Bridged Bis(cyclopentadienyl) Complexes of Molybdenum and Iron Carbonyls: Competitive Ring-to-Metal Migrations of Hydrogen and SiMe₂