Ammonia-borane, H3NBH3, is an intriguing molecule for chemical hydrogen storage applications. With both protic N-H and hydridic B-H bonds, three H atoms per main group element, and a low molecular weight, H3NBH3 has the potential to meet the stringent gravimetric and volumetric hydrogen storage capacity targets needed for transportation applications. Furthermore, devising an energy-efficient chemical process to regenerate H3NBH3 from dehydrogenated BNHx material is an important step towards realization of a sustainable transportation fuel. In this perspective we discuss current progress in catalysis research to control the rate and extent of hydrogen release and preliminary efforts at regeneration of H3NBH3.
In the presence of an iridium pincer complex, dehydrogenation of ammonia borane (H3NBH3) occurs rapidly at room temperature in tetrahydrofuran to generate 1.0 equivalent of H2 and [NH2BH2]5. A metal borohydride complex has been isolated as a dormant form of the catalyst which can be reactivated by reaction with H2.
In situ(11)B NMR monitoring, computational modeling, and external trapping studies show that selectivity and extent of H(2) release in metal-catalysed dehydrogenation of ammonia borane, NH(3)BH(3), are determined by coordination of reactive aminoborane, NH(2)BH(2), to the metal center.
Reaction of NaBH4 with (tBuPOCOP)IrHCl affords the previously reported complex (tBuPOCOP)IrH2(BH3) (1) (tBuPOCOP = kappa(3)-C6H3-1,3-[OP(tBu)2]2). The structure of 1 determined from neutron diffraction data contains a B-H sigma-bond to iridium with an elongated B-H bond distance of 1.45(5) A. Compound 1 crystallizes in the space group P1 (Z = 2) with a = 8.262 (5) A, b = 12.264 (5) A, c = 13.394 (4) A, and V = 1256.2 (1) A(3) (30 K). Complex 1 can also be prepared by reaction of BH3 x THF with (tBuPOCOP)IrH2. Reaction of (tBuPOCOP)IrH2 with pinacol borane gave initially complex 2, which is assigned a structure analogous to that of 1 based on spectroscopic measurements. Complex 2 evolves H2 at room temperature leading to the borane complex 3, which is formed cleanly when 2 is subjected to dynamic vacuum. The structure of 3 has been determined by X-ray diffraction and consists of the (tBuPOCOP)Ir core with a sigma-bound pinacol borane ligand in an approximately square planar complex. Compound 3 crystallizes in the space group C2/c (Z = 4) with a = 41.2238 (2) A, b = 11.1233 (2) A, c = 14.6122 (3) A, and V = 6700.21 (19) A(3) (130 K). Reaction of (tBuPOCOP)IrH2 with 9-borobicyclononane (9-BBN) affords complex 4. Complex 4 displays (1)H NMR resonances analogous to 1 and exists in equilibrium with (tBuPOCOP)IrH2 in THF solutions.
Reaction of [Cp*Ir(P-P)Cl][B(C6F5)4] (P-P = bisdimethydiphosphinomethane (dmpm), bisdiphenyldiphosphinomethane (dppm)) with [Et3Si][B(C6F5)4] in methylene chloride under 1 atm of hydrogen gas affords the dicationic compressed dihydride complexes [Cp*Ir(P-P)H2][B(C6F5)4]2. These dicationic complexes are highly acidic and are very readily deprotonated to the corresponding monohydride cations. When the preparative reaction is carried out under HD gas, the hydride resonance exhibits JHD = 7-9 Hz, depending upon the temperature of observation, with higher values of JHD observed at higher temperatures. A thermally labile rhodium analogue, [CpRh(dmpm)(H2)][B(C6F5)4]2, was prepared similarly. A sample prepared with HD gas gave JHD = 31 Hz and J(HRh) = 31 Hz, allowing the Rh complex to be identified as a dihydrogen complex. Quantum dynamics calculations on a density functional theory (DFT) potential energy surface have been used to explore the structure of the Ir complexes, with particular emphasis on the nature of the potential energy surface governing the interaction between the two hydride ligands and the Ir center.
Double take: A remarkable electron‐deficient cationic dihydride complex [Ir(ItBu)2(H)2](PF6) (see crystal structure), prepared in high yield from the reaction of 14‐electron complex [Ir(ItBu′)2](PF6) and H2 gas, shows a rare agostic interaction. The reaction illustrates the reversibility of a double, intramolecular CH activation process and provides a rare example of a “proposed” intermediate. ItBu: N,N′‐di(tert‐butyl)imidazol‐2‐ylidene.
Photolysis of solutions of M(CO)6 (M = Cr, Mo, and W) in the presence of Et3SiH affords the silane complexes Cr(CO)5(eta2-HSiEt3), Mo(CO)5(eta2-HSiEt3), and W(CO)5(eta2-HSiEt3). Observed values of J(SiH) in these complexes are consistent with modest elongation of the Si-H bond. With Ph3SiH, complexes of Cr(CO)5 and W(CO)5 were obtained, but no complex with Mo was observed. When Ph2SiH2 was employed, only one Si-H bond interacts with the metal center. A dynamic exchange process observable on the magnetic resonance time scale exchanges the pendant and coordinated Si-H bonds of the coordinated diphenylsilane. Silanes bound to M(CO)5 are activated with respect to reaction with nucleophiles. With methanol, catalytic methanolysis of HSiEt3 has been observed in the presence of Cr(CO)5(eta2-HSiEt3), affording Et3SiOMe.
Reaction of [Cp*Ir(dmpm)Cl]Cl with [Et3Si]B(ArF)4 (dmpm = bisdimethyl-phosphinomethane; ArF = C6F5) under hydrogen gas affords the dicationic complex [Cp*Ir(dmpm)H2]2+ (1), which is readily deprotonated by weak bases to give [Cp*Ir(dmpm)H]+. Complex 1 exists as a mixture of two isomers (97:3). On the basis of the magnitude of 2JH-P couplings and T1 measurements, a cis-dihydride or dihydrogen complex structure is suggested for the predominant isomer 1-cis (2JH-P = 6 Hz), with the minor isomer assigned a transoid structure 1-trans (2JH-P = 20 Hz). When the preparative reaction is carried out with HD gas, the resonance in the 1H NMR spectrum assigned to 1-cis-d1 exhibits1JH-D = 9.0 Hz. The observed values of 1JH-D vary significantly with temperature, increasing from 7.0 Hz at 223K to 9.0 Hz at 300 K. The observed chemical shift of 1-cis-d1 also varies significantly with temperature. These observations are interpreted in terms of a dynamic equilibrium between a cis-dihydride and a dihydrogen complex.
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