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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
NiN(2)S(2) complexes as metallodithiolate ligands to Rh(I), Rh(II) and Rh(III)
Stephen P Jeffery1, Kayla N Green, Marilyn V Rampersad
1Texas A and M University, Department of Chemistry, College Station, Texas 77843-3255, USA.
Abstract:
Three molecular structures are reported which utilize the NiN(2)S(2) ligands -, (bis(mercaptoethyl)diazacyclooctane)nickel and -', bis(mercaptoethyl)diazacycloheptane)nickel, as metallodithiolate ligands to rhodium in oxidation states i, ii and iii. For the Rh(I) complex, the NiN(2)S(2) unit behaves as a bidentate ligand to a square planar Rh(I)(CO)(PPh(3))(+) moiety with a hinge or dihedral angle (defined as the intersection of NiN(2)S(2) and S(2)Rh(C)(P) planes) of 115 degrees . Supported by -' ligands, the Rh(II) oxidation state occurs in a dirhodium C(4) paddlewheel complex wherein four NiN(2)S(2) units serve as bidentate bridging ligands to two singly-bonded Rh(II) ions at 2.893(8) A apart. A compilation of the remarkable range of M-M distances in paddlewheel complexes which use NiN(2)S(2) complexes as paddles is presented. The Rh(III) state is found as a tetrametallic [Rh(-')(3)](3+) cluster, roughly shaped like a boat propeller and structurally similar to tris(bipyridine)metal complexes.
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