3:;15712-13-7Relevant articles and documents
Octahedral d3 and d4 complexes of molybdenum with 1,2-bis(dimethylphosphino)ethane
Fong, Lawrence K.,Fox, James R.,Foxman, Bruce M.,Cooper, N. John
, p. 1880 - 1886 (2008/10/08)
Reaction of amorphous molybdenum dichloride with 1,2-bis(dimethylphosphino)ethane (dmpe) affords a convenient route to trans-[Mo(dmpe)2Cl2], while reaction of [Mo(CO)4Cl2] with dmpe leads to the formation of the seven-coordinate cation [Mo(dmpe)2(CO)2Cl]+, isolated as the PF6- salt and shown by a single-crystal X-ray diffraction study to have a capped-trigonal-prismatic geometry (orthorhombic space group Pnma, with a = 13.483 (3) ?, b = 11.065 (2) ?, c = 17.796 (3) ?, ρcalcd = 1.54 g cm-3, ρobsd = 1.54 g cm-3, Z = 4, and Rw = 3.83%). Cyclic voltammetry has established that the neutral dichloride is reversibly oxidized to trans-[Mo(dmpe)2Cl2]+ with (Ea + Ec)/2 = -0.510 V vs. SCE. The cation can be obtained as the PF6- salt if AgPF6 is the oxidant, or as the SnCl3- salt if SnCl2 is the oxidant. The d4 and d3 dichlorides have both been characterized by single-crystal X-ray diffraction studies: [Mo(dmpe)2Cl2] crystallizes in the monoclinic space group P21/c with a = 13.218 (3) ?, b = 12.640 (2) ?, c = 13.327 (3) ?, β = 93.18 (2)°, ρcalcd = 1.40 g cm-3, ρobsd = 1.42 g cm-3, Z = 4, and Rw = 3.22%, while [Mo(dmpe)2Cl2]SnCl3 crystallizes in the monoclinic space group P21/n with a = 14.756 (4) ?, b = 10.808 (2) ?, c = 18.572 (5) ?, β = 109.80 (2)°, ρcald = 1.65 g cm-3, ρobsd = 1.65 g cm-3, Z = 4, and Rw = 4.01%. Both have octahedral geometries with trans dichlorides. [Mo(dmpe)2Cl2] can be reduced by 40% sodium amalgam in the presence of N2 or CO to give [Mo(dmpe)2(N2)2] and [Mo(dmpe)2(CO)2], respectively, both of which are formed as a mixture of the cis and trans isomers.
