Transition metal complexes based on carboranyl ligands containing N, P, and S donors: Synthesis, reactivity and applications

Continuous study on preparation of multimetallic clusters is stimulated by their rich coordination chemistry and promising applications in a variety of interesting fields. Although numerous efforts have been devoted to this field, the rational design of homo- and hetero-multimetallic compounds with direct metal–metal bonding supported by 1,2-dicarba-closo-dodecarborane-1,2-dichalcogenolates will still be an important step forward. This tutorial review focuses on the synthetic approach via redox reactions between the pseudo-aromatic half-sandwich oraganometallic carborane precursors and low-valent transition metal reagents. The tailoring of reaction conditions and the structural information from the resulting products are discussed extensively.

Formation of direct metal–metal bonds from 16-electron “pseudo-aromatic” half-sandwich complexes Cp″M[E2C2(B10H10)]

Advances in the chemistry of organometallic complexes with 1,2-dichalcogenolato-o-carborane ligands

Cage CH⋯X interactions in solid-state structures of icosahedral carboranes

Transition metal-induced B–H functionalization of o-carborane

Addition Reactions of the Novel Mononuclear Dithio-o-carboranylcobalt(III) Complex (η5-C5H5)Co(η2-S2C2B10H10)

Synthesis, X-ray crystal structure, and reactivity of the monomeric dithio-o-carboranyl iridium complex [Ir(η5-C5Me5)(η2-S2C2B10H10)]

Syntheses and Crystal Structures of Intramolecularly Stabilized Organogallium Compounds Containing an o-Carboranyl C,N-Chelating Ligand System

The reaction of [M(μ-Cl)(cod)] 2 (M = Rh, Ir; cod = cycloocta-1,5-diene) with two equivalents of the lithium ortho -carboranethiolate derivative LiCab N,S 2 [LiCab N,S = closo -2-(dimethylaminomethyl)-1-(lithiumthiolato)- ortho -carborane] produced the four-coordinated metallacyclic compounds, Cab N,S M(cod) 3 (M = Rh 3a , Ir 3b ), in which the metal atom was stabilized via intramolecular N,S -coordination. These new compounds have been isolated in high yields and characterized by IR and NMR spectroscopy. The structure consists of an amino- ortho -carboranethiolate fragment bonded to (cod)Rh(I) via nitrogen and sulfur, so as to give the metal a square-planar environment. Subsequent carbonylation reactions of 3a , 3b result in the quantitative formation of the corresponding (amino- ortho -carboranethiolato)(carbonyl)metal N,S -chelates Cab N,S M(CO) 2 4 (M = Rh 4a , Ir 4b ). The metal carbonyl complexes 4a , 4b have been isolated and characterized by spectroscopic and compound 4a also by X-ray diffraction techniques. The molecular structure of 4a reveals that the rhodium atom is coordinated by nitrogen and sulfur atoms of the amino- ortho -carboranethiolate ligand, and two carbonyl ligands complete the coordination of the metal atom.

N,S-Chelating Amino-ortho-carboranethiolate Complexes of Rhodium and Iridium: Synthesis and Reactivity. X-Ray Crystal Structures of (η4-C8H12)Rh[(NMe2CH2)SC2B10H10] and (CO)2Rh[(NMe2CH2)SC2B10H10]

Synthesis and Characterization of o-Carboranylmethyleneamine and o-Carboranylmethylenephosphine. Crystal Structure of $(H_3B)(NMe_2CH_2CCH)$ and $(C_2B_{10}H_{11})CH_2PPh_2$

Kwonil Park

Papers

Addition Reactions of the Novel Mononuclear Dithio-o-carboranylcobalt(III) Complex (η5-C5H5)Co(η2-S2C2B10H10)

Synthesis, X-ray crystal structure, and reactivity of the monomeric dithio-o-carboranyl iridium complex [Ir(η5-C5Me5)(η2-S2C2B10H10)]

Syntheses and Crystal Structures of Intramolecularly Stabilized Organogallium Compounds Containing an o-Carboranyl C,N-Chelating Ligand System

N,S-Chelating Amino-ortho-carboranethiolate Complexes of Rhodium and Iridium: Synthesis and Reactivity. X-Ray Crystal Structures of (η4-C8H12)Rh[(NMe2CH2)SC2B10H10] and (CO)2Rh[(NMe2CH2)SC2B10H10]

Synthesis and Characterization of o-Carboranylmethyleneamine and o-Carboranylmethylenephosphine. Crystal Structure of $(H_3B)(NMe_2CH_2CCH)$ and $(C_2B_{10}H_{11})CH_2PPh_2$