TY - JOUR
T1 - Structure and reactivity of an intermediate in the two-electron reduction of dimolybdenum(III) by a hydride ligand in the MoHMo system
AU - Ardon, Michael
AU - Bino, Avi
PY - 1995/2
Y1 - 1995/2
N2 - The raaction between the μ-hydride dimolybdenum(III) complex [Mo2Cl8H]3- and carboxylic acids in aqueous solution produces a violet species which slowly decomposes to yield the quadruply bonded dimolybdenum(II) complex Mo2(O2CR)4. The violet intermediate in the reaction of [Mo2Cl8H]3- with glycine was isolated by ion exchange chromatography and crystallized. The crystals of [Mo2H(OH)(gly)2Cl4] (1) are monoclinic, space group P21/n with a = 9.536(4), b = 14.792(4), c = 9.339(3) A ̊, β = 109.99(3)°, V = 1283(1) A ̊3 and Z = 4. The two Mo(III) ions in this complex are bridged by one hydride ligand one OH- group and two glycine groups through the carboxylic end. The MoMo distance is 2.353(5) Å, the shortest found for the MoHMo system. [(H2O)2MoH(OH)(gly)2Mo(H2O)2]4+ is the structure proposed for the violet intermediate II in the reaction 4gly+[Mo2Cl8H]3-→ II→H++[Mo2(gly)4]Cl4+4Cl- This structure was derived from structure 1, the high ionic charge of about 4+ and the absence of chloride in this species. The decomposition reaction of II and the relation of II with the red intermediate III of the reaction [Mo2Cl8H]3-+H2O→III→H2+[Mo2(OH)2Cl2] 2++6 Cl-] +H+ is discussed.
AB - The raaction between the μ-hydride dimolybdenum(III) complex [Mo2Cl8H]3- and carboxylic acids in aqueous solution produces a violet species which slowly decomposes to yield the quadruply bonded dimolybdenum(II) complex Mo2(O2CR)4. The violet intermediate in the reaction of [Mo2Cl8H]3- with glycine was isolated by ion exchange chromatography and crystallized. The crystals of [Mo2H(OH)(gly)2Cl4] (1) are monoclinic, space group P21/n with a = 9.536(4), b = 14.792(4), c = 9.339(3) A ̊, β = 109.99(3)°, V = 1283(1) A ̊3 and Z = 4. The two Mo(III) ions in this complex are bridged by one hydride ligand one OH- group and two glycine groups through the carboxylic end. The MoMo distance is 2.353(5) Å, the shortest found for the MoHMo system. [(H2O)2MoH(OH)(gly)2Mo(H2O)2]4+ is the structure proposed for the violet intermediate II in the reaction 4gly+[Mo2Cl8H]3-→ II→H++[Mo2(gly)4]Cl4+4Cl- This structure was derived from structure 1, the high ionic charge of about 4+ and the absence of chloride in this species. The decomposition reaction of II and the relation of II with the red intermediate III of the reaction [Mo2Cl8H]3-+H2O→III→H2+[Mo2(OH)2Cl2] 2++6 Cl-] +H+ is discussed.
KW - Binuclear complexes
KW - Crystal structures
KW - Hydride complexes
KW - Molybdenum complexes
UR - http://www.scopus.com/inward/record.url?scp=0009101947&partnerID=8YFLogxK
U2 - 10.1016/0020-1693(94)04274-Y
DO - 10.1016/0020-1693(94)04274-Y
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AN - SCOPUS:0009101947
SN - 0020-1693
VL - 229
SP - 417
EP - 420
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1-2
ER -