Reactions of hydrazido(2-) and dinitrogen complexes of molybdenum with reducing agents. Crystal structure of a molybdenum(V) hydrazido(2-) complex: [MoBr[sub 3](NNH[sub 2])(Ph[sub 2]PCH[sub 2]CH[sub 2]PPh[sub 2])][center dot]THF

Journal Article · Wed Apr 28 04:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00061a028· OSTI ID:6260121

George, T A; Kaul, B B ^[1]; Chen, Qin; Zubieta, J ^[2]

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1. Univ. of Nebraska, Lincoln (United States)
2. Syracuse Univ., NY (United States)

Tin(II) halides and germanium(II) iodide (known two-electron-reducing agents) have been shown to be effective reducing agents in the transformation of nitrogen hydride intermediates derived from N[sub 2] into ammonia and hydrazine. Addition of SnX[sub 2] (X = Br, Cl), [Et[sub 4]N][SnCl[sub 3]], or GeI[sub 2] to a mixture of trans-[Mo(N[sub 2])[sub 2](PS-diphos)(PPh[sub 2]Me)[sub 2]] (PS-diphos = -P(Ph)CH[sub 2]CH[sub 2]PPh[sub 2] attached to polystyrene-2% divinylbenzene) and HBr in CH[sub 2]Cl[sub 2] (a mixture from which no ammonia is formed) causes substantial amounts of ammonia to be produced. Significant increases in the yield of ammonia were obtained when these same reducing agents were added to a mixture of trans-[Mo(N[sub 2])[sub 2](dppe)(PPh[sub 2]Me)[sub 2]] (1) (dppe = Ph[sub 2]PCH[sub 2]CH[sub 2]PPh[sub 2]) and HBr in CH[sub 2]Cl[sub 2]: yields (mol/mol of Mo) of NH[sub 3], N[sub 2]H[sub 4], and N[sub 2] changed from 0.39, 0.44, and 1.39 (100% N atom balance) in the absence of reducing agent to 1.24, 0.13, and 1.22 (99% N atom balance) in the presence of GeI[sub 2] (4 mol). This is ca. 300% increase in the yield of ammonia. The reactions of HX (X = Br, Cl) with 1 in THF and CH[sub 2]Cl[sub 2] in the presence of tin(II) species were investigated. Solid 1 reacted with HX (10 mol) to produce [MoX(NNH[sub 2])(dppe)(PPh[sub 2]Me)[sub 2]X], which was stable in MeOH but lost a phosphine ligand in both THF and CH[sub 2]Cl[sub 2] solution to form [MoX[sub 2](NNH[sub 2])(dppe)(PPh[sub 2]Me)]. Reaction of HX (6 mol) with 1 in THF in the presence of MX[sub 2] (M = Sn, Zn) produced the insoluble, crystalline molybdenum(V) hydrazido(2-) complex [MoX[sub 3](NNH[sub 2])(dppe)] (2) in high yield (X = Br, 82%, g = 2.03; X = Cl, 72%, g = 1.98). 25 refs., 1 fig., 3 tabs.

• OSTI ID: 6260121
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:9; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BROMIDES
BROMINE COMPOUNDS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
HALIDES
HALOGEN COMPOUNDS
HYDRAZIDES
LATTICE PARAMETERS
MOLECULAR STRUCTURE
MOLYBDENUM BROMIDES
MOLYBDENUM COMPLEXES
MOLYBDENUM COMPOUNDS
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN OXIDES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
REACTION INTERMEDIATES
REDUCING AGENTS
REDUCTION
REFRACTORY METAL COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
YIELDS