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

Journal Article · Wed Jun 09 00:00:00 EDT 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00064a030· OSTI ID:6000457

Vale, M G; Schrock, R R ^[1]

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1. Massachusetts Institute of Technology, Cambridge, MA (United States)

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.

• OSTI ID: 6000457
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:12; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

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