TY - JOUR
T1 - Synthesis, Characterization, and Reactivity of Molybdenum Organohydrazido(2-) Complexes with Phosphines as Ancillary Ligands. X-ray Structures of [Mo(NNPh2)2Cl2(PPh3)] and [Mo(NNMePh)2Cl2(PPh3)2]·0.5CH2Cl2
AU - Bustos, Carlos
AU - Manzur, Carolina
AU - Carrillo, David
AU - Robert, Francis
AU - Gouzerh, Pierre
PY - 1994/10/1
Y1 - 1994/10/1
N2 - The complexes [Mo(NNPh2)2Cl2(PPh3)] (3), [Mo(NNMePh)2Cl2(PPh3)2] (4), [Mo(NNRPh)2Cl2(PMePh2)2] (R = Ph, 5; R = Me, 6), [Mo(NNRPh)2Cl2(PMe2Ph)2] (R = Ph, 7; R = Me, 8), and [Mo(NNRPh)2Cl2(dppe)] (R = Ph, 9; R = Me, 10) have been obtained in good yields by reaction of [Mo(NHNRPh)(NNRPh)(acac)Cl2] (R = Me, 1; R = Ph, 2) with PMe3-nPhn (n = 1-3) or Ph2PCH2CH2PPh2 in acetonitrile. In refluxing toluene, 4 undergoes dissociation of a PPh3 ligand to give [Mo(NNMePh)2Cl2(PPh3)] (11). Complexes 3, 4, and 11 react with an excess of acetylacetone in refluxing acetonitrile to give back 1 or 2. Complexes 3-11 have been studied by 1H, 31P NMR, IR, and UV-visible spectroscopy and by electrochemistry. In addition, compounds 3 and 4·0.5CH2- Cl2 have been characterized by X-ray crystal analyses. Complex 3 is monoclinic, space group P21/c, with a = 21.787(5) Å, b = 17.638(1) Å, c = 20.066(14) Å, β = 95.32(1)°, and Z = 8. The structure was solved using 3965 unique observed reflections; the refinements of 735 variables gave final R and Rw values of 0.049 and 0.053, respectively. Compound 4·0.5CH2Cl2 is triclinic, space group P1, with a = 14.384(12) Å,b= 16.599(6) Å, c = 23.919(11) Å, α = 77.44(4)°, β = 77.51(1)°, γ = 64.39(2)°, and Z = 4. The structure was solved using 5456 unique observed reflections; the refinements of 901 variables converged to R and Rw values of 0.070 and 0.083, respectively. Complex 3 displays a distorted trigonal bipyramidal geometry with the cis-hydrazido ligands in the equatorial plane, while 4 displays a distorted octahedral geometry with cis-hydrazido and trans-phosphine ligands.
AB - The complexes [Mo(NNPh2)2Cl2(PPh3)] (3), [Mo(NNMePh)2Cl2(PPh3)2] (4), [Mo(NNRPh)2Cl2(PMePh2)2] (R = Ph, 5; R = Me, 6), [Mo(NNRPh)2Cl2(PMe2Ph)2] (R = Ph, 7; R = Me, 8), and [Mo(NNRPh)2Cl2(dppe)] (R = Ph, 9; R = Me, 10) have been obtained in good yields by reaction of [Mo(NHNRPh)(NNRPh)(acac)Cl2] (R = Me, 1; R = Ph, 2) with PMe3-nPhn (n = 1-3) or Ph2PCH2CH2PPh2 in acetonitrile. In refluxing toluene, 4 undergoes dissociation of a PPh3 ligand to give [Mo(NNMePh)2Cl2(PPh3)] (11). Complexes 3, 4, and 11 react with an excess of acetylacetone in refluxing acetonitrile to give back 1 or 2. Complexes 3-11 have been studied by 1H, 31P NMR, IR, and UV-visible spectroscopy and by electrochemistry. In addition, compounds 3 and 4·0.5CH2- Cl2 have been characterized by X-ray crystal analyses. Complex 3 is monoclinic, space group P21/c, with a = 21.787(5) Å, b = 17.638(1) Å, c = 20.066(14) Å, β = 95.32(1)°, and Z = 8. The structure was solved using 3965 unique observed reflections; the refinements of 735 variables gave final R and Rw values of 0.049 and 0.053, respectively. Compound 4·0.5CH2Cl2 is triclinic, space group P1, with a = 14.384(12) Å,b= 16.599(6) Å, c = 23.919(11) Å, α = 77.44(4)°, β = 77.51(1)°, γ = 64.39(2)°, and Z = 4. The structure was solved using 5456 unique observed reflections; the refinements of 901 variables converged to R and Rw values of 0.070 and 0.083, respectively. Complex 3 displays a distorted trigonal bipyramidal geometry with the cis-hydrazido ligands in the equatorial plane, while 4 displays a distorted octahedral geometry with cis-hydrazido and trans-phosphine ligands.
UR - http://www.scopus.com/inward/record.url?scp=0011722774&partnerID=8YFLogxK
U2 - 10.1021/ic00100a017
DO - 10.1021/ic00100a017
M3 - Article
AN - SCOPUS:0011722774
SN - 0020-1669
VL - 33
SP - 4937
EP - 4944
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 22
ER -