Bis(allenylidene) Complexes of Palladium and Platinum | Zendy

Florian Kessler | Zendy; B. Weibert | Zendy; Helmut Fischer | Zendy

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Bis(allenylidene) Complexes of Palladium and Platinum

Author(s) -

Florian Kessler,

B. Weibert,

Helmut Fischer

Publication year - 2010

Publication title -

organometallics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.231

H-Index - 172

eISSN - 1520-6041

pISSN - 0276-7333

DOI - 10.1021/om100346x

Subject(s) - chemistry , transmetalation , palladium , platinum , medicinal chemistry , ligand (biochemistry) , stereochemistry , cis–trans isomerism , alkylation , catalysis , organic chemistry , biochemistry , receptor

trans-Bis(alkynyl)palladium complexes, trans-[(PEt3)2Pd(−C≡CC{═O}NR2)2] (NR2 = NMe2 (2a), N(CH2)4 (2b)), were synthesized by two different methods: (a) by copper-catalyzed reaction of HC≡CC(═O)NR2 with [PdCl2(PEt3)2] under basic conditions and (b) by treating HC≡CC(═O)NR2 with AgNO3 followed by transmetalation of the alkynyl ligand from silver to [PdCl2(PEt3)2]. The reaction of AgC≡CC(═O)NMe2 (3a) with trans-[Br(PiPr3)2PdC≡CC(═O)N(CH2)4] (5) affords a complex containing two different alkynyl ligands, trans-[(PiPr3)2Pd{−C≡CC(═O)NMe2}{−C≡CC(═O)N(CH2)4}] (6). Methylation of 2a,b and 6 with MeOTf or [Me3O]BF4 yields dicationic bisallenylidene complexes of palladium, trans-[(PEt3)2Pd{═C═C═C(OMe)NR2}2]2+ 2X− (X = OTf, BF4; NR2 = NMe2, N(CH2)4) and trans-[(PEt3)2Pd{═C═C═C(OMe)NMe2}{═C═C═C(OMe)N(CH2)4}]2+2OTf− (7-OTf). In contrast to the reaction of 3a with [PdCl2(PEt3)2], that of 3a with the platinum complex [PtCl2(PPh3)2] gives cis- and trans-[(PPh3)2Pt(−C≡CC{═O}NMe2)2] (8a (cis) and 9a (trans)), depending on t...

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