NiN(2)S(2) complexes as metallodithiolate ligands to Rh(I), Rh(II) and Rh(III).
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.
Jeffery
Stephen P
SP
Texas A and M University, Department of Chemistry, College Station, Texas 77843-3255, USA.
Green
Kayla N
KN
Rampersad
Marilyn V
MV
Reibenspies
Joseph H
JH
Darensbourg
Marcetta Y
MY
D008024:Ligands; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry
D008024:Ligands; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D009532:Nickel; D012238:Rhodium