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Title: Synthesis and reactions of monomeric hydrazine and hydrazido complexes that contain the Cp*MoMe[sub 3] core

Abstract

Addition of N[sub 2]H[sub 4], N[sub 2]H[sub 3]Me, NH[sub 2]NMe[sub 2], or NHMeNHMe to Cp*MoMe[sub 3](OTf) yields complexes of the type [Cp*MOMe[sub 3](N[sub 2]H[sub x]Me[sub y])]OTf. Attempted deprotonation of cationic Mo(V) adducts that contain methylhydrazine or 1,1-dimethylhydrazine yields Cp*MoMe[sub 3](NNMeH) and Cp*MoMe[sub 3](NNMe[sub 2]) in ca. 50% yield, but attempted deprotonation of [Cp*MoMe[sub 3](NH[sub 2]NH[sub 2])]OTf yields no recognizable products. Hydrazido(2[minus]) complexes also can be prepared by adding methylhydrazine or 1, 1-dimethylhydrazine to [Cp*MoMe[sub 3](OAr)]PF[sub 6]. Cp*MoMe[sub 3](NNMeH) reacts with butyllithium to give Cp*MoMe[sub 3](NNMeLi), a yellow-orange crystalline solid that decomposes in the solid state in a matter of hours. Addition of triethylamine to [Cp*MoMe[sub 3](NHMeNHMe)]OTf gives [Cp*MoMe[sub 3](NMeNMeH)]OTf in ca. 50% yield. Addition of HX (X = Cl, OTf, BF[sub 4], B[3,5-C[sub 6]H[sub 3](CF[sub 3])[sub 2]][sub 4]) to Cp*MoMe[sub 3](NNRR') complexes (R = Me; R' = H, Me) yields Cp*MoMe[sub 2]X(NNRR') complexes. Methyl triflate reacts with Cp*MoMe[sub 3](NNMe[sub 2]) to yield [Cp*MoMe[sub 3](NNMe[sub 3])][sup +]. [Cp*MoMe[sub 3](NH[sub 2]NH[sub 2])][sup +] is reduced by zing amalgam in the presence of 2,6-lutidine hydrochloride to give 1.84 equiv of ammonia. [Cp*MoMe[sub 3](NH[sub 2]NH[sub 2])][sup +] also is a catalyst for the reduction of hydrazine to ammonia under similar conditions. Although decomposition reactionsmore » that involve loss of a methyl group in part complicate the chemistry of Cp*MoMe[sub 3] relative to that of Cp*WMe[sub 3], controlled cleavage of the N-N bond and catalytic reduction of hydrazine in the Mo system suggest that there is no significant difference between Mo and W as far as reduction of the N-N bond beyond the hydrazido(2[minus]) stage is concerned.« less

Authors:
;  [1]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States)
Publication Date:
OSTI Identifier:
6000457
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 32:12; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MOLYBDENUM COMPLEXES; CHEMICAL PREPARATION; ORGANOMETALLIC COMPOUNDS; AMMONIA; CATALYSTS; CATALYTIC EFFECTS; CHEMICAL REACTION YIELD; HOMOGENEOUS CATALYSIS; HYDRAZIDES; HYDRAZINE; REDUCTION; CATALYSIS; CHEMICAL REACTIONS; COMPLEXES; HYDRIDES; HYDROGEN COMPOUNDS; NITROGEN COMPOUNDS; NITROGEN HYDRIDES; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; YIELDS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Vale, M G, and Schrock, R R. Synthesis and reactions of monomeric hydrazine and hydrazido complexes that contain the Cp*MoMe[sub 3] core. United States: N. p., 1993. Web. doi:10.1021/ic00064a030.
Vale, M G, & Schrock, R R. Synthesis and reactions of monomeric hydrazine and hydrazido complexes that contain the Cp*MoMe[sub 3] core. United States. https://doi.org/10.1021/ic00064a030
Vale, M G, and Schrock, R R. Wed . "Synthesis and reactions of monomeric hydrazine and hydrazido complexes that contain the Cp*MoMe[sub 3] core". United States. https://doi.org/10.1021/ic00064a030.
@article{osti_6000457,
title = {Synthesis and reactions of monomeric hydrazine and hydrazido complexes that contain the Cp*MoMe[sub 3] core},
author = {Vale, M G and Schrock, R R},
abstractNote = {Addition of N[sub 2]H[sub 4], N[sub 2]H[sub 3]Me, NH[sub 2]NMe[sub 2], or NHMeNHMe to Cp*MoMe[sub 3](OTf) yields complexes of the type [Cp*MOMe[sub 3](N[sub 2]H[sub x]Me[sub y])]OTf. Attempted deprotonation of cationic Mo(V) adducts that contain methylhydrazine or 1,1-dimethylhydrazine yields Cp*MoMe[sub 3](NNMeH) and Cp*MoMe[sub 3](NNMe[sub 2]) in ca. 50% yield, but attempted deprotonation of [Cp*MoMe[sub 3](NH[sub 2]NH[sub 2])]OTf yields no recognizable products. Hydrazido(2[minus]) complexes also can be prepared by adding methylhydrazine or 1, 1-dimethylhydrazine to [Cp*MoMe[sub 3](OAr)]PF[sub 6]. Cp*MoMe[sub 3](NNMeH) reacts with butyllithium to give Cp*MoMe[sub 3](NNMeLi), a yellow-orange crystalline solid that decomposes in the solid state in a matter of hours. Addition of triethylamine to [Cp*MoMe[sub 3](NHMeNHMe)]OTf gives [Cp*MoMe[sub 3](NMeNMeH)]OTf in ca. 50% yield. Addition of HX (X = Cl, OTf, BF[sub 4], B[3,5-C[sub 6]H[sub 3](CF[sub 3])[sub 2]][sub 4]) to Cp*MoMe[sub 3](NNRR') complexes (R = Me; R' = H, Me) yields Cp*MoMe[sub 2]X(NNRR') complexes. Methyl triflate reacts with Cp*MoMe[sub 3](NNMe[sub 2]) to yield [Cp*MoMe[sub 3](NNMe[sub 3])][sup +]. [Cp*MoMe[sub 3](NH[sub 2]NH[sub 2])][sup +] is reduced by zing amalgam in the presence of 2,6-lutidine hydrochloride to give 1.84 equiv of ammonia. [Cp*MoMe[sub 3](NH[sub 2]NH[sub 2])][sup +] also is a catalyst for the reduction of hydrazine to ammonia under similar conditions. Although decomposition reactions that involve loss of a methyl group in part complicate the chemistry of Cp*MoMe[sub 3] relative to that of Cp*WMe[sub 3], controlled cleavage of the N-N bond and catalytic reduction of hydrazine in the Mo system suggest that there is no significant difference between Mo and W as far as reduction of the N-N bond beyond the hydrazido(2[minus]) stage is concerned.},
doi = {10.1021/ic00064a030},
url = {https://www.osti.gov/biblio/6000457}, journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 32:12,
place = {United States},
year = {1993},
month = {6}
}