Cyclopalladated azido complexes containing C,N-donor (HC~N = 2-(2'-thienyl)pyridine, azobenzene, 3,3'-dimethyl azobenzene, N,N'-dimethylbenzylamine, 2-phenylpyridine) ligands: reactivity towards organic unsaturated compounds and catalytic properties

Title
Cyclopalladated azido complexes containing C,N-donor (HC~N = 2-(2'-thienyl)pyridine, azobenzene, 3,3'-dimethyl azobenzene, N,N'-dimethylbenzylamine, 2-phenylpyridine) ligands: reactivity towards organic unsaturated compounds and catalytic properties
Authors
이경은전형탁한삼용함정엽김용주Soon W. Lee
Keywords
Cyclopalladated; azido complex; C~N chelating; C,N-donor ligand
Issue Date
2009-09
Publisher
Dalton transactions : an international journal of inorganic chemistry / RSoC
Citation
VOL 33, 6578-6592
Abstract
Cyclopalladated azido dimers having various C,N-donor ligands, [Pd(m-N3)(C,N-Ln)]2 (L1H = 2-(2¢-thienyl)pyridine; L2H = azobenzene; L3H = 3,3¢-dimethylazobenzene; L4H = N,N¢-dimethylbenzylamine; L5H = 2-phenylpyridine), underwent cleavage with tertiary (or chelating) phosphines to form the cyclopalladated [Pd(N3)(PR3)(C,N-L)], the s-bonded [Pd(N3)(PR3)2(C-L)], or the dinuclearcyclopalladated [PdN3(PR3)(C,N-L)]2(m-P~P) complexes. In particular, treating [Pd(m-N3)(C,N-L)]2 with the basic chelating phosphine (depe or dmpe) produced the homoleptic bis(chelating) complex [Pd(C,N-Ln)2] (n = 1–3). Complex [Pd(N3)(PR3)(C,N-L4)] or [Pd(N3)(PR3)2(C-L4)] reacted with aryl isocyanides to selectively give the imidoyl [Pd(N3)(–C=N–Ar)(PR3)(N-L4)] or the imidoyl carbodiimido complex [Pd(N=C=N–Ar)(–C=N–Ar)(PR3)(N-L4)], which was formed by the CN–Ar insertion into the orthometallated Pd–C bond on the phenyl moiety or the interaction into the Pd–N3 bond of the supporting ligand. In addition, reactions of [Pd(N3)(PR3)2(C-Ln)] (n = 1, 2, 4) with R–NCS {R = i-Pr, C6H4–NCS, (CH3)3Si} gave the S-coordinated tetrazole–thiolato Pd(II) complexes. Finally, the catalytic activity of the cyclopalladated azido complexes was evaluated.
URI
http://pubs.kist.re.kr/handle/201004/35696
ISSN
1477-9226
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