Issue 31, 2017

Synthesis and characterization of 1′-(diphenylphosphino)-1-isocyanoferrocene, an organometallic ligand combining two different soft donor moieties, and its Group 11 metal complexes

Abstract

The development of a practical synthesis of 1′-(diphenylphosphino)-1-aminoferrocene (2) and its P-borane adduct (2B) allowed the facile preparation of 1′-(diphenylphosphino)-1-isocyanoferrocene (1). This compound combining two specific soft-donor moieties was studied as a ligand for univalent Group 11 metal ions. The reactions of 1 with AgCl at 1 : 1 and 2 : 1 molar ratios only led to the coordination polymer [Ag2(μ-Cl)2(μ(P,C)-1)]n (6), while those with Ag[SbF6] provided the dimer [Ag2(Me2CO-κO)2(μ(P,C)-1)2][SbF6]2 and the quadruply-bridged disilver complex [Ag2(μ(P,C)-1)4][SbF6]2 (8), respectively. Addition of 1 to [AuCl(tht)] (tht = tetrahydrothiophene) afforded the mono- and the digold complex, [AuCl(1P)] (9) and [(μ(P,C)-1)(AuCl)2] (10), depending on the reaction stoichiometry. Finally, the reaction of 1 with [Au(tht)2][SbF6] or halogenide removal from 9 with AgNTf2 led to cationic dimers [Au2(μ(P,C)-1)2]X2 (11, X = SbF6 (a) or NTf2 (b)). Catalytic tests in the Au-mediated isomerization of (Z)-3-methylpent-2-en-4-yn-1-ol to 2,3-dimethylfuran revealed that 11a and 11b are substantially less catalytically active than their analogues containing 1′-(diphenylphosphino)-1-cyanoferrocene as the ligand, most likely due to a stronger coordination of the isonitrile moiety, which prevents dissociation of the dimeric complexes into catalytically active monomeric species.

Graphical abstract: Synthesis and characterization of 1′-(diphenylphosphino)-1-isocyanoferrocene, an organometallic ligand combining two different soft donor moieties, and its Group 11 metal complexes

Supplementary files

Article information

Article type
Paper
Submitted
28 Jun 2017
Accepted
16 Jul 2017
First published
18 Jul 2017
This article is Open Access
Creative Commons BY license

Dalton Trans., 2017,46, 10339-10354

Synthesis and characterization of 1′-(diphenylphosphino)-1-isocyanoferrocene, an organometallic ligand combining two different soft donor moieties, and its Group 11 metal complexes

K. Škoch, I. Císařová, J. Schulz, U. Siemeling and P. Štěpnička, Dalton Trans., 2017, 46, 10339 DOI: 10.1039/C7DT02336G

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