Phosphorus as Lone Pair Donor and Ligand Acceptor: A Paddlewheel with Ru←P Axis | Zendy

Gericke Robert | Zendy; Wagler Jörg | Zendy

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Phosphorus as Lone Pair Donor and Ligand Acceptor: A Paddlewheel with Ru←P Axis

Author(s) -

Gericke Robert,

Wagler Jörg

Publication year - 2018

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.201701386

Subject(s) - hexacoordinate , chemistry , lone pair , ligand (biochemistry) , crystallography , natural bond orbital , ruthenium , hydride , stereochemistry , molecule , computational chemistry , metal , density functional theory , catalysis , biochemistry , receptor , organic chemistry , silicon

[Ru(PyO) 2 (nbd)] ( 1 ) (PyO = 2‐pyridyloxy, nbd = norbornadiene) and PhP(PyO) 2 react with formation of complex [PhP(µ‐PyO) 3 Ru(κ‐PyO)] ( 2 ), which features a Ru–P bond between a pentacoordinate P atom and a hexacoordinate Ru atom, bridged by three PyO ligands. Addition of CO leads to opening of the Ru(κ‐PyO) chelate with formation of complex [PhP(µ‐PyO) 4 Ru(CO)] ( 3 ), a paddlewheel‐shaped complex with a Ru–P bond between a hexacoordinate P atom and a hexacoordinate Ru atom, bridged by four PyO ligands. In complexes 2 and 3 the P atom serves as a lone pair donor toward Ru. Interestingly, the P atom also serves as a ligand acceptor, thus enhancing its coordination number and generating a coordination site at Ru. These complexes were studied by multinuclear NMR spectroscopy, cyclic voltammetry, and quantum chemical calculations (NBO/NLMO analyses).

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