The Staudinger reaction of platinum(II)- and palladium(II)-coordinated 2-(azidomethyl)phenyl isocyanide. X-ray structure of trans-[PtCl{(H)}(PPh3)2][BF4] · CDCl3 · H2O
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- 作者：Basato ; Marino ; Benetollo ; Franco ; Facchin ; Giacomo ; Michelin ; Rino A. ; Mozzon ; Mirto ; Pugliese ; Sandra ; et. al.
- 关键词：Functionalized isocyanides ; Transition metal complexes ; N-heterocyclic carbene complexes
- 刊名：Journal of Organometallic Chemistry
- 出版年：2004
- 出版时间：January 15, 2004
- 年：2004
- 卷：689
- 期：2
- 页码：454-462
- 全文大小：290 K
文摘
2-(Azidomethyl)phenyl isocyanide, 2-(CH2N3)C6H4N
C (AziNC), coordinates to some cationic Pt(II) and Pd(II) species to afford isocyanide complexes of the type trans-[MCl(AziNC)(PPh3)2][BF4] (M=Pt, l; Pd, 2). AziNC is coordinated also in some neutral Pt(II) and Pd(II) species such as [MCl2(AziNC)2] (M=Pt, 3; Pd, 4) derived from the reactions of 2 equiv. of AziNC with [PtCl2(COD)] and [PdCl2(MeCN)2], respectively. Complexes 1 and 2 react with 1 equiv. of PPh3 affording the heterocyclic carbene complexes trans-[MCl{<inline-fig BASELINE=""0.0""><link locator=""fx10""></inline-fig>(H)}(PPh3)2][BF4] (M=Pt, 5; Pd, 6). Complexes 3 and 4 react with 1 equiv. of PPh3 displacing the isocyanide with the formation of the complexes cis-[MCl2(AziNC)(PPh3)] (M=Pt, 7; Pd, 8). These latter ones react with 2 equiv. of PPh3 affording as the final products the cationic carbene species trans-[MCl{<inline-fig BASELINE=""0.0""><link locator=""fx10""></inline-fig>(H)}(PPh3)2][Cl] (M=Pt, 9; Pd, 10). Complex 5 was also characterized by single crystal X-ray diffraction. The carbene complex is square-planar and the angle formed between the platinum square plane and the heterocyclic carbene ligand is 87.9(2)°. The C(1)–N(1) and C(1)–N(2) bond distances in the latter of 1.32(2) and 1.30(2) Å, respectively, are short for a single bond and indicate extensive π-bonding between the nitrogen atoms and the carbene carbon.
C (AziNC), coordinates to some cationic Pt(II) and Pd(II) species to afford isocyanide complexes of the type trans-[MCl(AziNC)(PPh3)2][BF4] (M=Pt, l; Pd, 2). AziNC is coordinated also in some neutral Pt(II) and Pd(II) species such as [MCl2(AziNC)2] (M=Pt, 3; Pd, 4) derived from the reactions of 2 equiv. of AziNC with [PtCl2(COD)] and [PdCl2(MeCN)2], respectively. Complexes 1 and 2 react with 1 equiv. of PPh3 affording the heterocyclic carbene complexes trans-[MCl{<inline-fig BASELINE=""0.0""><link locator=""fx10""></inline-fig>(H)}(PPh3)2][BF4] (M=Pt, 5; Pd, 6). Complexes 3 and 4 react with 1 equiv. of PPh3 displacing the isocyanide with the formation of the complexes cis-[MCl2(AziNC)(PPh3)] (M=Pt, 7; Pd, 8). These latter ones react with 2 equiv. of PPh3 affording as the final products the cationic carbene species trans-[MCl{<inline-fig BASELINE=""0.0""><link locator=""fx10""></inline-fig>(H)}(PPh3)2][Cl] (M=Pt, 9; Pd, 10). Complex 5 was also characterized by single crystal X-ray diffraction. The carbene complex is square-planar and the angle formed between the platinum square plane and the heterocyclic carbene ligand is 87.9(2)°. The C(1)–N(1) and C(1)–N(2) bond distances in the latter of 1.32(2) and 1.30(2) Å, respectively, are short for a single bond and indicate extensive π-bonding between the nitrogen atoms and the carbene carbon.