File(s) not publicly available
Metallaboratranes: Bis- and Tris(methimazolyl)borane Complexes of Group 9 Metal Carbonyls and Thiocarbonyls
journal contribution
posted on 2023-06-08, 00:02 authored by Ian CrossleyIan Crossley, Anthony F Hill, Anthony C WillisThe iridium poly(methimazolyl)borane complexes [IrH(CE)(PPh3){3-B,S,S0-B(mt)2R}](IrfB)8 (mt=methimazolyl=2-mercapto-3-methylimidazol-1-yl; E=O, S; R=mt, H) are described in detail. For R = mt, these materials are elucidated as paradigms for the final mechanistic intermediate in metallaboratrane formation, a role illustrated through hydride abstraction to afford the cationic salts [Ir(CE)(PPh3){4-B(mt)3}]X(IrfB)8 (E=O, S; X=Cl, BF4). The rhodium poly(methimazolyl)borate complexes [Rh(CO)(PPh3){2-S,S0-HB(mt)2R}] (R=mt, H) are also reported. These compounds are obtained in preference to the respective borane complexes (analogous to iridium); however [Rh(CO)- (PPh3){2-S,S0-HB(mt)3}] is observed to undergo facile solution-phase conversion to [Rh(CO)(PPh3)- {4-B,S,S0,S00-B(mt)3}]Cl(RhfB)8 in chlorinated solvents. The ramifications of these results,with respect to metallaboratrane formation, are discussed, substantiating previous mechanistic conjecture. In an attempt to establish an alternative route to iridaboratranes, the first isolable tris(methimazolyl)borate complex of iridium, cis,cis-[IrHCl(PPh3)2{2-S,S0-HB(mt)3], is reported and shown not to evolve to the iridaboratrane [IrCl(PPh3){4-B(mt)3}](IrfB)8 under conditions that lead to the corresponding rhodaboratrane. Factors are discussed that may contribute to this fine balance between the formation of methimazolylborate and methimazolylborane complexes.
History
Publication status
- Published
Journal
OrganometallicsISSN
0276-7333External DOI
Issue
2Volume
29Page range
326-336Pages
11.0Department affiliated with
- Chemistry Publications
Full text available
- No
Peer reviewed?
- Yes
Legacy Posted Date
2012-02-06Usage metrics
Categories
No categories selectedKeywords
Licence
Exports
RefWorks
BibTeX
Ref. manager
Endnote
DataCite
NLM
DC