Transition metal borohydride complexes. II. Th reaction of copper(I) compounds with boron hydride anions

Abstract

lutidine with triethylalane have been reported as calorimetrically determined in «-decane.24 For (C2-Hó)3A1• NC5H5, AH, = -21.2 kcal/mole, and for (02 6)3 1• 06 3(0 3)2, AH¡ = -18.0 kcal/mole.These enthalpy values do not include a correction for the enthalpy of dimerization of triethylalane. This value has been reported as -16.93 ± 0.23 kcal/mole in hexadecane.26 Since triethylalane is about 10-11% dissociated in a hydrocarbon solvent at ambient temperatures, one can only calculate the maximum enthalpy value by making the correction based on 100% dimerization of the triethylalane. Corrected in this way, these enthalpies become -29.7 kcal/mole for pyridine and -26.5 kcal/mole for 2,6-lutidine. These are surprising results since it is expected that triethylalane would have significantly larger frontal interaction than trimethylalane. The pyridines are generally weaker donors toward trimethylalane than the methylamines or ammonia but are comparable to (26) W.

Synthesis and Reactivity of Functionalized Binary and Ternary Thiometallate Complexes [(RT)4S6], [(RSn)3S4]2−, [(RT)2(CuPPh3)6S6], and [(RSn)6(OMe)6Cu2S6]4− (R=C2H4COOH, CMe2CH2COMe; T=Ge, Sn)

“…Future work will include the extension of studies considering related systems in order to wrap multinary chalcogenidometallate complexes and clusters by a bio-organic shell or to link them to each other through organic bridges with specific properties. [27] Cl 3 GeCH 2 CH 2 COOH, Cl 3 GeCMe 2 CH 2 -A C H T U N G T R E N N U N G COMe, [28] CuClPPh 2 Me, [29] and CuClA C H T U N G T R E N N U N G (PPh 3 ) 3 [30] were prepared according to the reported methods. CuCl, N 2 H 4 ·H 2 O and Na 2 S·9 H 2 O were purchased from Aldrich.…”

Hydrogen storage methods

“…Steric effects have also been suggested to be important in some compounds (Lippard and Ucko 1968). The special feature exhibited by the covalent metal hydroborides is that the hydroboride group is bonded to the metal atom by bridging hydrogen atoms similar to the bonding in diborane, which may be regarded as the simplest of the so called "electron-deficient" molecules.…”

Hydrogen density in nanostructured carbon, metals and complex materials

“…Steric effects have also been suggested to be important in some compounds [49,50]. The special feature exhibited by the covalent metal hydroborides is that the hydroboride group is bonded to the metal atom by bridging hydrogen atoms similar to the bonding in diborane, which may be regarded as the simplest of the so called "electron-deficient" molecules.…”

“…Such molecules possess fewer electrons than those apparently required to fill all the bonding orbital's, based on the criterion that a normal bonding orbital involving two atoms contains two electrons. The molecular orbital bonding scheme for diborane has been discussed extensively [49].…”