Journal
CHEMISTRYOPEN
Volume 11, Issue 3, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/open.202100224
Keywords
bisphosphine; cluster compounds; coinage metals; metal-metal interactions; N; P ligands
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Funding
- German Federal Ministry for Economic Affairs and Energy [ZF4477702SL7]
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The coordination behavior of a flexible and sterically demanding ligand (bqmpp) with Cu-I, Ag-I, and Au-I species was investigated. The X-ray crystal structures revealed interesting coordination geometries, including distorted square planar and square pyramidal geometries for Cu(I) compounds and the presence of Cu4Cl3 clusters in one of the complexes.
The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine (bqmpp) towards selected Cu-I, Ag-I and Au-I species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)(4)]BF4, compound 1 [Cu-2(bqmpp)(2)](BF4)(2) is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and pi-stacking of the ligand allow for a short Cu...Cu distance (2.588(9) angstrom). Cu-I complex 2 [Cu4Cl3(bqmpp)(2)]BF4 contains a rarely observed Cu4Cl3 cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu...Cu distances (2.447(1) angstrom) are present. The reaction of Ag[SbF6] with the ligand leads to a dinuclear compound (3) in solution as confirmed by P-31{H-1} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3, a tris(quinoline-2-ylmethyl)bisphenyl-phosphine (tqmbp) compound [Ag-2(tqmbp)(2)](SbF6)(2) 4 is formed by elimination of quinaldine. The Au(I) compound [Au-2(bqmpp)(2)]PF6 (5) is prepared as expected and shows a linear arrangement of two phosphine ligands around Au-I.
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