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Title: 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

Abstract

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 presencemore » 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.« less

Authors:
;  [1]; ;  [2]
  1. Univ. of Nebraska, Lincoln (United States)
  2. Syracuse Univ., NY (United States)
Publication Date:
OSTI Identifier:
6260121
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 32:9; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MOLYBDENUM BROMIDES; CHEMICAL PREPARATION; MOLYBDENUM COMPLEXES; REDUCTION; CHEMICAL REACTION YIELD; CHEMICAL REACTIONS; CRYSTAL STRUCTURE; HYDRAZIDES; LATTICE PARAMETERS; MOLECULAR STRUCTURE; NITRIC OXIDE; PHOSPHINES; REACTION INTERMEDIATES; REDUCING AGENTS; BROMIDES; BROMINE COMPOUNDS; CHALCOGENIDES; COMPLEXES; HALIDES; HALOGEN COMPOUNDS; MOLYBDENUM COMPOUNDS; NITROGEN COMPOUNDS; NITROGEN OXIDES; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; PHOSPHORUS COMPOUNDS; REFRACTORY METAL COMPOUNDS; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENT COMPOUNDS; YIELDS; 400201* - Chemical & Physicochemical Properties

Citation Formats

George, T A, Kaul, B B, Chen, Qin, and Zubieta, J. 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. United States: N. p., 1993. Web. doi:10.1021/ic00061a028.
George, T A, Kaul, B B, Chen, Qin, & Zubieta, J. 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. United States. https://doi.org/10.1021/ic00061a028
George, T A, Kaul, B B, Chen, Qin, and Zubieta, J. Wed . "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". United States. https://doi.org/10.1021/ic00061a028.
@article{osti_6260121,
title = {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},
author = {George, T A and Kaul, B B and Chen, Qin and Zubieta, J},
abstractNote = {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.},
doi = {10.1021/ic00061a028},
url = {https://www.osti.gov/biblio/6260121}, journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 32:9,
place = {United States},
year = {1993},
month = {4}
}