Heterometallic Transition‐Metal Complexes Based on 1‐Carboxy‐1′‐(diphenylphosphanyl)ferrocene, (tmeda/pmdta)Zinc(II), and Gold(I) Units

The synthesis of the Zn II and Ti IV carboxylates [L n M(O 2 CfcPPh 2 ) 2 ] {L n M = (tmeda)Zn ( 3 ); L n M = (pmdta)Zn ( 8 ); L n M = [Ti] ( 12 ); fc = (η 5 ‐C 5 H 4 ) 2 Fe; tmeda = N , N , N′ , N′ ‐ t etra m ethyl e thylene d i a mine; pmdta = 1,1,4,7,7‐ p enta m ethyl d iethylen t ri a mine; [Ti] = (η 5 ‐C 5 H 5 ) 2 Ti} and [L n M(X)(O 2 CfcPPh 2 )] {L n M = (pmdta)Zn, X = Cl ( 7 ); L n M = [Ti], X = Me ( 10 )} is reported. The reaction of Hdpf ( 1 ) {Hdpf = (η 5 ‐C 5 H 4 CO 2 H)(η 5 ‐C 5 H 4 PPh 2 )Fe} with [(tht)AuCl] ( 13 ) (tht = t etra h ydro t hiophene) gave [(Hdpf)AuCl] ( 14 ). Treatment of 3 , 7 , and 10 with 13 produced trimetallic [L n M(X){(O 2 CfcPPh 2 )AuCl}] {L n M = [Ti], X = Me ( 15 ); L n M = (pmdta)Zn, X = Cl ( 16 )} or [(tmeda)Zn{(O 2 CfcPPh 2 )AuCl} 2 ] ( 17 ). Heptametallic complexes were accessible by the reaction of 14 with HC≡CR {R = Fc, Rc; Fc = (η 5 ‐C 5 H 4 )(η 5 ‐C 5 H 5 )Fe; Rc = (η 5 ‐C 5 H 4 )(η 5 ‐C 5 H 5 )Ru}, whereby [(H 2 NEt 2 ){(O 2 CfcPPh 2 )AuCl}] ( 18 ) and [(H 2 NEt 2 ){(O 2 CfcPPh 2 )AuC≡CR}] {R = Fc ( 20a ), Rc ( 20b )} were formed. Further reaction of 20a and 20b with [(tmeda)ZnCl 2 ] ( 2 ) gave [(tmeda)Zn{(O 2 CfcPPh 2 )AuC≡CR} 2 ] {R = Fc ( 21a ), Rc ( 21b )}. The solid‐state structures of 3 , 7 , 12 , and 18 were determined by single‐crystal X‐ray diffraction. The Zn atom in 3 is in a distorted tetrahedral environment, while in 7 it is part of a distorted bipyramidal arrangement. In 18 , a stairlike 1D chain is built from three independent molecules of 18 by N–H ··· O hydrogen bonds and π–π interactions between phenyl or cyclopentadienyl rings of adjacent molecules. The cyclovoltammetric properties of 3 , 7 , 14 , 16 , 17 , 18 , 21a , and 21b are reported.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)