N,S-chelating amino-ortho-carboranethiolate complexes of rhodium and iridium: Synthesis and reactivity. X-ray crystal structures of (eta(4)-C8H12)Rh[(NMe2CH2)SC2B10H10] and (CO)(2)Rh[(NMe2CH2)SC2B10H10]

Citation
Sw. Chung et al., N,S-chelating amino-ortho-carboranethiolate complexes of rhodium and iridium: Synthesis and reactivity. X-ray crystal structures of (eta(4)-C8H12)Rh[(NMe2CH2)SC2B10H10] and (CO)(2)Rh[(NMe2CH2)SC2B10H10], COLL CZECH, 64(5), 1999, pp. 883-894
Citations number
18
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry
Journal title
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS
ISSN journal
0010-0765 → ACNP
Volume
64
Issue
5
Year of publication
1999
Pages
883 - 894
Database
ISI
SICI code
0010-0765(199905)64:5<883:NACORA>2.0.ZU;2-W
Abstract
The reaction of [M(mu-Cl)(cod)](2) (M = Rh, Ir; cod = cycloocta-1,5-diene) with two equivalents of the lithium ortho-calboranethiolate derivative LiCa b(N,S) 2 [LiCab(N,S) = closo-2-(dimethylaminomethyl)-1-(lithiumthiolato)-or tho-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 con sists 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 for mation 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 comp lexes 4a, 4b have been isolated and characterized by spectroscopic and comp ound 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 compl ete the coordination of the metal atom.