Group-12 metal complexes with isomeric 1-(diphenylphosphino)-1′-[N-(pyridylmethyl)carbamoyl]ferrocenes: coordination polymers vs. finite multinuclear coordination assemblies

Abstract

The isomeric ferrocene phosphine-carboxamides, 1-(diphenylphosphino)-1'-{[N-(2-pyridyl)-methyl]carbamoyl}ferrocene (1) and 1-(diphenylphosphino)-1'-{[N-(4-pyridyl)methyl]carbamoyl}ferrocene (2) have been studied as ligands in group-12 metal bromide complexes. The reactions of 1 with CdBr2 x 4H2O and HgBr(2) at 1:1 mole ratio gave the discrete tetracadmium complex [Cd2(micro-Br)2(-1kappa2O,N2)2[micro-1kappa2O,N2:2kappaP-(C5H4N)CH2NHC(O)fcPPh2-CdBr3]2] (7; fc = ferrocene-1,1'-diyl) and the halogeno-bridged dimer [[Hg(micro-Br)Br(-kappaP)]2] (8), respectively. In the presence of acetic acid, the CdBr2-1 system furnished a zwitterionic complex featuring protonated 1 as the P-monodentate donor, [CdBr3[Ph2PfcC(O)NHCH2(C5H4NH)-kappaP]] x H2O (6 x H2O). Under neutral conditions, compound , whose terminal donor groups are better arranged for the formation of extended assemblies, gave rise to one-dimensional coordination polymers [MBr2[micro(P,N)-]](n) (M = Cd, 4; M = Hg, ). The crystal structures of 2 x H2O, its corresponding phosphine oxide (3 x H2O), and complexes 4, 5, 6 x H2O, and have been determined, revealing extensive hydrogen bonding interactions in the solid state.

A new tris(ferrocenylamine) ditertiary phosphine: Synthesis and co-ordination studies

“…Concentrated HCl was added dropwise until effervescence subsided, the solvent volume reduced in vacuo and aqueous NaOH solution (2.5 g, 60 mL) added. The resulting suspension was stirred briefly and the organic phase extracted into CHCl 3 (60 mL), dried over anhydrous MgSO 4 3.02 (d, 4H, 2 J PH 3.6 Hz, CH 2 P). Attempts to obtain an analytically pure sample of 3 were unsuccessful.…”

“…terminal (PeFc) or as a backbone connector (PeFceP). Consequently the incorporation of a Fc moiety has allowed the preparation of various functionalised ferrocenyl phosphine [4,5], diphosphine [6,7] and polyphosphine [8,9] or macrocyclic [10] ligands to be realised. Considerable interest in ferrocenyl phosphines continues as a result of their interesting catalytic [11e14] and cytotoxic [15,16] properties.…”

“…Cyclic voltammogram of 1 in dry CH 2 Cl 2 , 0.1 M [NBu 4 ][BF4 ] at a scan rate of 50 mV s À1 . Suggested reduction potential (E pc ) of bridging ferrocenyl moiety (*).…”

Ferrocene‐Containing Coordination Polymers: Ligand Design and Assembled Structures

“…The combination of L25 and CdBr 2 produces a 1D coordination polymer [(CdBr 2 ) 2 ( L25 ) 2 ] n ( 90 ) (Figure 34b), in which L25 acts as an O 1 , P 2 ‐bridging ligand. In the structure, macrocycles, constructed of two anticlinal L25 ligands and two Cd II ions, are linked by a halogen bridge 55b. This is in contrast with related Zn II and Hg II complexes, which show 1:1 and 2:2 M/L discrete structures, respectively 55b.…”

“…In the structure, macrocycles, constructed of two anticlinal L25 ligands and two Cd II ions, are linked by a halogen bridge 55b. This is in contrast with related Zn II and Hg II complexes, which show 1:1 and 2:2 M/L discrete structures, respectively 55b. The structure of the Hg II complex closely resembles the local structure of 90 .…”