Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Chizhevsky, I. T.

doi:10.1016/j.ccr.2007.02.011

Cited by 50 publications

(6 citation statements)

References 98 publications

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“…2). 2 This study established that complex 4 is the structural isomer of 3 and, in addition, confirmed the agostic structure of this species. In fact, isomeric complexes 3 and 4 proved to be differing in the hapticities of the g-C 10 H 13 ligand with regard to the metal atom.…”

Section: Introductionsupporting

confidence: 74%

“…This is particularly surprising taking into account that the [7-R 3 N-nido-7-CB 10 H 10 ] 2À ligands are isoelectronic with the [nido-7,n-C 2 B 9 H 11 ] 2À (n = 8 or 9) dianions which are known to form numerous transition-metal metallacarborane complexes with mono-and polycyclic diolefins or their derivatives [2]. We now report the synthesis and spectroscopic characterization of the first two (g-dicyclopentenyl)-closo-rhodacarboranes derived from 11-vertex monocarbon carborane (1), viz.…”

Section: Introductionmentioning

confidence: 95%

“…[8] and metallacarborane complexes [9] with the g 3 -cycloalkenyltype ligands are well documented in the literature, to our best knowledge, complex 4 is, at present, the first such transition metal species among those having tricyclic carbocycles g-C 10 H n (n = 11-13) [2,7].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and structural characterization of isomeric monocarbon (η-dicyclopentenyl)-closo-rhodacarboranes stabilized by the agostic bonding interaction

Pisareva

Dolgushin

Godovikov

et al. 2008

Inorganic Chemistry Communications

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Section: Introductionsupporting

confidence: 74%

Section: Introductionmentioning

confidence: 95%

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Synthesis and structural characterization of isomeric monocarbon (η-dicyclopentenyl)-closo-rhodacarboranes stabilized by the agostic bonding interaction

Pisareva

Dolgushin

Godovikov

et al. 2008

Inorganic Chemistry Communications

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“…Since the discovery of 1,2-dicarba- closo -dodecaborane in the 1960s, research interest in carboranyl- and carbollide-based transition-metal complexes has greatly increased due to their high thermal and chemical stabilities . Their various applications in the fields of BNCT (boron–neutron capture therapy), catalysis, nuclear-waste remediation, and ion-selective electrodes have also been developed.…”

Section: Introductionmentioning

confidence: 99%

Monophosphine-o-Carborane Sulfide as a Noninnocent Ligand for C,S, S,S′, and B,S,S′ Coordination Modes of Half-Sandwich Iridium and Rhodium Complexes

Yao

Jin

2011

Organometallics

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Half-sandwich iridium and rhodium complexes with three different coordination modes were successfully synthesized by using the monophosphine-o-carborane sulfide 1-SPPh2-1,2-closo-C2B10H11 (1) as the ligand. Treatments of the dimeric metal complexes [Cp*M(μ-Cl)Cl]2 (M = Ir, Rh; Cp* = η5-C5Me5) with the lithium salt of monophosphine-o-carborane sulfide generate the C,S-coordinated complexes [Cp*IrCl(Cab C,S )] (2) and [Cp*RhCl(Cab C,S )] (3) (Cab C,S = (1-SPPh2-1,2-closo- C2B10H10)−), respectively. Compound 1 can be modified to give the corresponding thiol 1-SH-2-SPPh2-1,2-closo-C2B10H10 (4). The unexpected B,S,S′ coordination mode product [Cp*Ir(Cab B,S,S′)] (5) (Cab B,S,S′ = (η1-S′)(η1-SPPh2)(η1-1,2-closo-C2B10H9)) through B–H activation was obtained by the reaction of [Cp*Ir(μ-Cl)Cl]2 with the lithium salt of 4. However, [Cp*Rh(μ-Cl)Cl]2 gave the product [Cp*RhCl(Cab S,S′)] (6) (Cab S,S′ = (1-S′-2-SPPh2-1,2-closo- C2B10H10)−) with the S,S′ mode under the same conditions. When it was heated in CH3OH, complex 6 gradually transformed from a closo-carborane complex to the zwitterionic nido-carborane complex [Cp*Rh(7-S′-8-(SPPh2)-7,8-C2B9H10)] (7). They represent the first examples of half-sandwich complexes incorporating a monophosphine-o-carborane sulfide ligand. In addition, the iridium complex 2 exhibits catalytic activity up to 1.40 × 106 g of PNB (mol of Ir)−1 h–1 for the polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst. All complexes were fully characterized by elemental analysis and IR and NMR spectroscopy. The structures of 1, 2, and 5–7 were further confirmed by single-crystal X-ray diffraction.

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“…Carborane derivatives have been widely used in the fields of catalysis, − polymers, nonlinear optical materials, and BNCT (boron–neutron capture therapy) techniques, because of their versatile properties and the exceptionally stable carborane backbone . Recent reports on unusually stable C,N-, C,P-, C,S-, N,P-, N,S-, P,P- and S,S-chelating o -carboranyl metal complexes imply that the o -carboranyl ligand backbone could largely stabilize metal intermediates in organometallic reactions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Reactivity, and Structural Transformation of Mono- and Binuclear Carboranylamidinate-Based 3d Metal Complexes and Metallacarborane Derivatives

Yao

Jin

2012

Organometallics

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A series of carboranylamidinate-based 3d metal complexes are reported. Treatments of 3d metal dichlorides (CoCl2, NiCl2(DME), CuCl2) with the lithium salts of carboranylamidines (Cab N H) generate the mononuclear C,N-coordinated complexes [(RNC(closo-1,2-C2B10H10)(NHR)]2M (1–6; M  Co, Ni, Cu; R = iPr, Cy) in moderate yields, respectively. These complexes have similar structures in the solid state, in which the metal atom is coordinated to two nitrogen atoms and bonded to two cage carbon atoms in a distorted-tetrahedral geometry. As a noninnocent ligand, Cab N H can be modified to produce carboranylamidinate thiol (Cab N SH) and nido derivatives Dcab N H (9, 10), respectively. Reaction of cupric acetate with 1 equiv of Cab N SH gave the binuclear complexes {[RNC(closo-1,2-C2B10H10)(NHR)]SCu}2 (R = iPr (7), Cy (8)) in 66 and 63% yields, respectively. The structure of 7 shows the formation of a Cu–Cu bond, and the geometry of the Cu2S2 core is planar. The zwitterionic nickel dicarbollide complexes (Dcab N )Ni(PPh3)Cl (11, 12) were prepared by reactions of the lithium salts of Dcab N H (9, 10) with NiCl2(PPh3)2 in THF. All complexes were characterized by elemental analysis and IR and NMR spectroscopy. The structures of 1, 3–5, 7, and 9–11 were further confirmed by single-crystal X-ray diffraction.

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Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Cited by 50 publications

References 98 publications

Synthesis and structural characterization of isomeric monocarbon (η-dicyclopentenyl)-closo-rhodacarboranes stabilized by the agostic bonding interaction

Synthesis and structural characterization of isomeric monocarbon (η-dicyclopentenyl)-closo-rhodacarboranes stabilized by the agostic bonding interaction

Monophosphine-o-Carborane Sulfide as a Noninnocent Ligand for C,S, S,S′, and B,S,S′ Coordination Modes of Half-Sandwich Iridium and Rhodium Complexes

Synthesis, Reactivity, and Structural Transformation of Mono- and Binuclear Carboranylamidinate-Based 3d Metal Complexes and Metallacarborane Derivatives

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