skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds

Abstract

Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H{sub 2} gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe){sub 2}, dmpe = 1,2-bis(dimethylphosphinoethane) was capable of reducing a variety of BX{sub 3} compounds having hydride affinity (HA) greater than or equal to HA of BEt{sub 3}. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, (HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +}), to form B-H bonds. The hydride donor abilities ({Delta}G{sub H{sup -}}{sup o}) of HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +} were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX{sub 3} compounds. The collective data guided our selection of BX{sub 3} compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe){sub 2} was observed to transfer H{sup -} to BX{sub 3} compounds with X = H, OC{sub 6}F{sub 5} and SPh. The reaction with B(SPh){sub 3} is accompanied by formation of (BH{sub 3}){sub 2}-dmpe and (BH{sub 2}SPh){sub 2}-dmpe products that follow from reductionmore » of multiple BSPh bonds and loss of a dmpe ligand from Co. Reactions between HCo(dmpe){sub 2} and B(SPh){sub 3} in the presence of triethylamine result in formation of Et{sub 3}N-BH{sub 2}SPh and Et{sub 3}N-BH{sub 3} with no loss of dmpe ligand. Reactions of the cationic complex [HNi(dmpe){sub 2}]{sup +} with B(SPh){sub 3} under analogous conditions give Et{sub 3}N-BH{sub 2}SPh as the final product along with the nickel-thiolate complex [Ni(dmpe){sub 2}(SPh)]{sup +}. The synthesis and characterization of HCo(dedpe){sub 2} (dedpe = diethyldiphenyl(phosphino)ethane) from H{sub 2} and a base is also discussed; including the formation of an uncommon trans dihydride species, trans-[(H{sub 2})Co(dedpe){sub 2}][BF{sub 4}].« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1033061
Report Number(s):
PNNL-SA-79240
Journal ID: ISSN 0020-1669; INOCAJ; EB4202000; TRN: US201202%%563
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 50; Journal Issue: 23; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; ACETONITRILE; AFFINITY; AMMONIA; CLEAVAGE; COBALT; HYDRIDES; HYDROGEN STORAGE; NICKEL HYDRIDES; REGENERATION; SYNTHESIS; TRANSFER REACTIONS; TRANSITION ELEMENTS; hydride transfer; transition metal; cobalt; nickel; GAUSSIAN-BASIS SETS; CORRELATED MOLECULAR CALCULATIONS; AMMONIA-BORANE; DONOR ABILITIES; HYDROGEN; PROTON; NI; FEH(DMPE)2(BH4)

Citation Formats

Mock, Michael T, Potter, Robert G, O'Hagan, Molly J, Camaioni, Donald M, Dougherty, William G, Kassel, W S, and DuBois, Daniel L. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds. United States: N. p., 2011. Web. doi:10.1021/ic200857x.
Mock, Michael T, Potter, Robert G, O'Hagan, Molly J, Camaioni, Donald M, Dougherty, William G, Kassel, W S, & DuBois, Daniel L. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds. United States. https://doi.org/10.1021/ic200857x
Mock, Michael T, Potter, Robert G, O'Hagan, Molly J, Camaioni, Donald M, Dougherty, William G, Kassel, W S, and DuBois, Daniel L. 2011. "Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds". United States. https://doi.org/10.1021/ic200857x.
@article{osti_1033061,
title = {Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds},
author = {Mock, Michael T and Potter, Robert G and O'Hagan, Molly J and Camaioni, Donald M and Dougherty, William G and Kassel, W S and DuBois, Daniel L},
abstractNote = {Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H{sub 2} gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe){sub 2}, dmpe = 1,2-bis(dimethylphosphinoethane) was capable of reducing a variety of BX{sub 3} compounds having hydride affinity (HA) greater than or equal to HA of BEt{sub 3}. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, (HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +}), to form B-H bonds. The hydride donor abilities ({Delta}G{sub H{sup -}}{sup o}) of HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +} were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX{sub 3} compounds. The collective data guided our selection of BX{sub 3} compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe){sub 2} was observed to transfer H{sup -} to BX{sub 3} compounds with X = H, OC{sub 6}F{sub 5} and SPh. The reaction with B(SPh){sub 3} is accompanied by formation of (BH{sub 3}){sub 2}-dmpe and (BH{sub 2}SPh){sub 2}-dmpe products that follow from reduction of multiple BSPh bonds and loss of a dmpe ligand from Co. Reactions between HCo(dmpe){sub 2} and B(SPh){sub 3} in the presence of triethylamine result in formation of Et{sub 3}N-BH{sub 2}SPh and Et{sub 3}N-BH{sub 3} with no loss of dmpe ligand. Reactions of the cationic complex [HNi(dmpe){sub 2}]{sup +} with B(SPh){sub 3} under analogous conditions give Et{sub 3}N-BH{sub 2}SPh as the final product along with the nickel-thiolate complex [Ni(dmpe){sub 2}(SPh)]{sup +}. The synthesis and characterization of HCo(dedpe){sub 2} (dedpe = diethyldiphenyl(phosphino)ethane) from H{sub 2} and a base is also discussed; including the formation of an uncommon trans dihydride species, trans-[(H{sub 2})Co(dedpe){sub 2}][BF{sub 4}].},
doi = {10.1021/ic200857x},
url = {https://www.osti.gov/biblio/1033061}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 23,
volume = 50,
place = {United States},
year = {2011},
month = {12}
}