title: Synthesis of phosphinoferrocene amides and thioamides from carbamoyl chlorides and the structural chemistry of Group 11 metal complexes with these mixed-donor ligands.
abstract: The reaction of in situ generated 1'-(diphenylphosphino)-1-lithioferrocene with carbamoyl chlorides, ClC(E)NMe2, affords the corresponding (thio)amides, Ph2PfcC(E)NMe2 (E = O (), S (); fc = ferrocene-1,1'-diyl). These compounds as well as their analogues, Ph2PfcC(O)NHMe () and Ph2PfcC(O)NH2 (), prepared from 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) were studied as ligands for the Group 11 metal ions. In the reactions with [Cu(MeCN)4][BF4], the amides give rise to bis-chelate complexes of the type [Cu(L-κ(2)O,P)2][BF4]. Similar products, [Ag(L-κ(2)O,P)2]ClO4, are obtained from silver(i) perchlorate and , or . In contrast, the reaction of AgClO4 with produces a unique molecular dimer [Ag()(ClO4-κO)]2, where the metal centres are bridged by the sulfur atoms of the P,S-chelating thioamides. The reactions of with [AuCl(tht)] (tht = tetrahydrothiophene) afford the expected gold(i)-phosphine complexes, [AuCl(L-κP)], containing uncoordinated (thio)amide moieties. Hemilabile coordination of the phosphinoamide ligands in complexes with the soft Group 11 metal ions is established by the crystal structure of a solvento complex, [Cu(-κ(2)O,P)(-κP)(CHCl3-κCl)][BF4], which was isolated serendipitously during an attempted crystallisation of [Cu(-κ(2)O,P)2][BF4]. All of the compounds are characterised by spectroscopic methods, and the structures of several representatives of both the free phosphinoamides and their complexes are determined by X-ray diffraction analysis and further studied by DFT calculations and cyclic voltammetry.
authors.affiliation: Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Prague 2, Czech Republic. stepnic@natur.cuni.cz.
authors.forename: Tiago A
authors.initials: TA
authors.lastname: Fernandes
authors.forename: Hana
authors.initials: H
authors.lastname: Solařová
authors.forename: Ivana
authors.initials: I
authors.lastname: Císařová
authors.forename: Filip
authors.initials: F
authors.lastname: Uhlík
authors.forename: Martin
authors.initials: M
authors.lastname: Štícha
authors.forename: Petr
authors.initials: P
authors.lastname: Štěpnička
mesh_terms: D000577:Amides / Q000138:chemical synthesis*; D002219:Carbamates / Q000138:chemical synthesis*; D002712:Chlorides / Q000138:chemical synthesis*; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000138:chemical synthesis*; D008024:Ligands; D000075163:Metallocenes; D010720:Phosphines / Q000138:chemical synthesis*; D013854:Thioamides / Q000138:chemical synthesis*
chemical_list: D000577:Amides; D002219:Carbamates; D002712:Chlorides; D005296:Ferrous Compounds; D008024:Ligands; D000075163:Metallocenes; D010720:Phosphines; D013854:Thioamides; C070766:carbamic acid; C004998:ferrocene