Tetrahydroborates halides

To effect reduction to the parent heterocycle, a solution of the dichloro compound in DMF was being added to a hot solution of sodium tetrahydroborate in the same solvent, when a violent explosion occurred [1,2]. This may have arisen either from interaction of the dichloro compound with the solvent, or from the known instability of hot solutions of the tetrahydroborate in DMF. Use of aqueous diglyme as an alternative solvent [3] would only be applicable to this and other hydrolytically stable halides [2],... 

The diethyl ester of phenylphosphonous acid (diethoxyphenyl-phosphine) provides an easy pathway to relatively stable telrakis complexes of zero- and low-valent transition metals.1,2 Anhydrous metal halides serve as the metal source for the complexes, avoiding the necessity of inconvenient starting materials such as nickel carbonyl. The nickel(O) complex is formed by reaction with the phosphonite in ethanol with the addition of sodium tetrahydroborate, relatively stable dihydridoiron(l I) and hydridocobalt(I) complexes are obtained. 

Alkali-metal tetrahydraborate reduction of phosphorus halides is of limited utility . Lithium tetrahydroborate reaction with PClj or PClj in Et20 at — 80°C produces PHj, but yields are low" ... 

The ability of phosphines to act as both a metal oxidation states and as a 7r acceptor to relieve electron density from lower metal oxidation states explains, in part, the observation that diphosphines stabilize the +3, +1, and 0 oxidation states at the expense of the +2 oxidation state.870 Vanadium(II) diphosphine halides, [V(dmpe)2X2] (dmpe = dimethyl-dimethylphosphinoethane, X = Br or I), were prepared as side products in the synthesis of [XV(CO)2(dmpe)2].885 The structurally characterized diphosphino V11 tetrahydroborate complex, tra .s-[V(BH4)2(dmpe)2], (223) was synthesized via the reduction of similar vanadium(III) precursors.832 The reaction of a vanadium(II) chloride salt with dmpe afforded the tra s-[VCl2(dmpe)2] complex which can be alkylated with MeLi or MgMe2 to afford the organometallic trans-[V(Me)2(dm pcVJ compound, which in turn reacts with thiocyanate to form tnms -[V(NCS)2(dmpe)2].8 87 Acetonitrile or propionitrile readily displace the chlorides from trans- WCl2(dmpe)2] to form // tf/ ,v-[V( NCR)2(dmpc)2][BI>h4]2 (R = Me or Et) the acetonitrile derivative reacts with HCPh(S02CF3)2 in acetonitrile solvent to yield the hexaacetonitrile species [V(NCMe)6]2+.887... 

Zirconium and hafnium diboride have been studied less extensively. Zirconium diboride potentially is useful as a coating for solar absorbers [242]. These compositions can be prepared either by hydrogen co-reduction of the metal and boron halides [242], or by the decomposition of the metal tetrakis(tetrahydroborates) M(BH4)4 [241]. 

X-ray powder diffraction data reveal that CP3UCI and Cp3ThCl are isomor-phous. Tris(cyclopentadienyl)thorium derivatives of other halides, alkoxides, tetrahydroborates, etc., can be prepared in a manner analogous to the uranium reaction above [58]. Tris(cyclopentadienyl)neptunium chloride, Cp3NpCl, can be prepared either by a radiochemical synthesis [75] ... 

The compounds (r/-CsHs)3UCl and (r/-CsHs)3ThCl are useful precursors for the synthesis of a large number of organoactinides, such as tris(cyclopentadienyl)metal alkoxides, tetrahydroborates, alkyls and aryls, halides, amides, and other derivatives,The chlorouranium compound was first synthesized by Reynolds and Wilkinson in 1956 from uranium tetrachloride and sodium cyclopentadienide in tetrahydrofuran. Vacuum sublimation, in our hands, invariably gives the pure product in low yield. The thorium analog was originally prepared in a similar manner,... 

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