Reaction of Cp*MoCl[sub 4] and Cp*WCl[sub 4] with H[sub 2]O, H[sub 2]S, amines, and hydrazines. Formation of the trioxo anions [Cp*Mo(O)[sub 3]][sup [minus]] and [Cp*W(O)[sub 3]][sup [minus]] and the trisulfido anion [Cp*W(S)[sub 3]][sup [minus]]

Journal Article · Wed Sep 01 04:00:00 EDT 1993 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00033a015· OSTI ID:5651894

Rau, M S; Kretz, C M; Geoffroy, G L ^[1]; Rheingold, A L ^[2]

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1. Pennsylvania State Univ., University Park, PA (United States)
2. Univ. of Delaware, Newark, DE (United States)

Both Cp*WCl[sub 4] and Cp*MoCL[sub 4] react with aqueous Bu[sup t]NH[sub 2] in the presence of air to form the trioxo anions [Cp*M(O)[sub 3]][sup [minus]], which have been isolated as their [Bu[sup t]NH[sub 3]][sup +] salts. The trioxo anions are also produced upon treatment of Cp*M(O)[sub 2]Cl or [Cp*M(O)[sub 2]][sub 2]([mu]-O) with aqueous Bu[sup t]NH[sub 2]. [Ph[sub 3]P[sub 2]N][sup +] and [Bu[sup n] [sub 4]N][sup +] salts of [Cp*W(O)[sub 3]][sup [minus]] were obtained by metathesis reactions, and the reaction of [Bu[sup t]NH[sub 3]][Cp*W(O)[sub 3]] with EtC[CO]CH=CH[sub 2] gave the salt [Bu[sup t](EtC[O]CH[sub 2]CH[sub 2])NH[sub 2]][Cp* W(O)[sub 3]]. The complex Cp*WCl[sub 4] was also observed to react with anhydrous Bu[sup t]NH[sub 2] in the absence of air to form Cp*W(NBu[sup t])Cl[sub 2], which in turn gave Cp*W(O)(NBu[sup t])Cl upon exposure to moist air. With phenylhydrazine, Cp*WCl[sub 4] reacted in air to give the bis(hydrazinido) complex Cp*W(NNHPh)[sub 2]Cl. With H[sub 2]S in air, both Cp*WCl[sub 4] and Cp*MoCl[sub 4] reacted to give mixtures of the known dinuclear compounds [Cp*M(S)][sub 2]([mu]-S)[sub 2] and [Cp*M(S)][sub 2]([mu]-S[sub 2]), but in the presence of NEt[sub 3], Cp*WCl[sub 4] and H[sub 2]S reacted to give the new trisulfido anion [Cp*W(S)[sub 3]][sup [minus]]. 40 refs., 5 figs., 12 tabs.

• OSTI ID: 5651894
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:9; ISSN 0276-7333; ISSN ORGND7
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
AMINES
ANIONS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
HYDRAZINE
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
INFORMATION
IONS
MOLECULAR STRUCTURE
MOLYBDENUM COMPLEXES
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXYGEN COMPOUNDS
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
WATER