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Synthesis and Coordination Chemistry of the New Unsymmetrical Ligand Ph 2 PCH 2 NHC 6 H 4 PPh 2
Author(s) -
Zhang Qingzhi,
Aucott Stephen M.,
Slawin Alexandra M. Z.,
Woollins J. Derek
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200207)2002:7<1635::aid-ejic1635>3.0.co;2-b
Subject(s) - chemistry , coordination complex , ligand (biochemistry) , combinatorial chemistry , nanotechnology , organic chemistry , biochemistry , metal , receptor , materials science
Condensation of Ph 2 PCH 2 OH with 2‐(diphenylphosphanyl)aniline in toluene gave the new unsymmetrical ligand Ph 2 PCH 2 NHC 6 H 4 PPh 2 ( 1 ) in good yield. Oxidation of 1 with H 2 O 2 or elemental sulfur led to the oxidised products Ph 2 P(O)CH 2 NHC 6 H 4 P(O)Ph 2 ( 2 ) and Ph 2 P(S)CH 2 NHC 6 H 4 P(S)Ph 2 ( 3 ). The new ligand 1 demonstrates three distinct modes of coordination. Reaction of compound 1 with [MX 2 (cod)] (M = Pd, Pt; X = Cl, Br, Me) or [Mo(CO) 4 (pip) 2 ] gave the chelate complexes [PdCl 2 (Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A )] ( 4 ), [PdBr 2 (Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A )] ( 5 ), [PtCl 2 (Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A )] ( 6 ), [PtMe 2 (Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A )] ( 7 ) and [Mo(CO) 4 (Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A )] ( 8 ). Coordination of 1 with [{RuCl(μ‐Cl)(η 3 :η 3 ‐C 10 H 16 )} 2 ] or [{RhCl(μ‐Cl)(η 5 ‐C 5 Me 5 )} 2 ] gave the monodentate complexes [RuCl 2 (η 3 :η 3 ‐C 10 H 16 )(Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X )] ( 9 ) and [RhCl 2 (η 5 ‐C 5 Me 5 )(Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X )] ( 10 ). Reaction of 1 with [{IrCl(μ‐Cl)(η 5 ‐C 5 Me 5 )} 2 ] led to a mixture from which the monodentate complex [IrCl 2 (η 5 ‐C 5 Me 5 )(Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X )] ( 11) and the chelate cationic complex [IrCl(η 5 ‐C 5 Me 5 )(Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A )][Cl] ( 12) were separated . Abstraction of the chloride ligands from complexes 9 and 10 with AgClO 4 gave the cationic chelate complexes [RuCl(η 3 :η 3 ‐C 10 H 16 )(Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A )][ClO 4 ] ( 13 ) and [RhCl(η 5 ‐C 5 Me 5 )(Ph 2 PCH 2 NHC 6 H 4 PPh 2 ‐ P X , P A ][ClO 4 ] ( 14 ). Compound 1 also functions as a bridging ligand when reacted with two molar equivalents of [AuCl(tht)] or one molar equivalent of [{RhCl(μ‐Cl)(η 5 ‐C 5 Me 5 )} 2 ] to give the bimetallic complexes [Ph 2 P{AuCl}CH 2 NHC 6 H 4 PPh 2 {AuCl}] ( 15) and [{RhCl 2 (η 5 ‐C 5 Me 5 )} 2 (Ph 2 PCH 2 NHC 6 H 4 PPh 2 )] ( 16 ). The dioxidised compounds 2 and 3 and several typical complexes 8 , 9 , 11 and 14 were structurally characterised by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)