Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds

Michael T. Mock, Robert G. Potter, Molly J. O'Hagan, Donald M. Camaioni, William G. Dougherty, W. Scott Kassel, Daniel L DuBois

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H2 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)2 (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX3 compounds having a hydride affinity (HA) greater than or equal to the HA of BEt3. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)2 and [HNi(dmpe)2]+, to form B-H bonds. The hydride donor abilities (ΔGH-°) of HCo(dmpe)2 and [HNi(dmpe)2]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX3 compounds. The collective data guided our selection of BX3 compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)2 was observed to transfer H- to BX3 compounds with X = H, OC6F5, and SPh. The reaction with B(SPh)3 is accompanied by the formation of dmpe-(BH3)2 and dmpe-(BH2(SPh))2 products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)2 and B(SPh)3 in the presence of triethylamine result in the formation of Et3N-BH2SPh and Et 3N-BH3 with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)2]+ with B(SPh)3 under analogous conditions give Et3N-BH2SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)2(SPh)] +. The synthesis and characterization of HCo(dedpe)2 (dedpe = Et2PCH2CH2PPh2) from H 2 and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)2Co(dedpe) 2][BF4].

Original languageEnglish
Pages (from-to)11914-11928
Number of pages15
JournalInorganic Chemistry
Volume50
Issue number23
DOIs
Publication statusPublished - Dec 5 2011

Fingerprint

Cobalt
Nickel
Hydrides
hydrides
cobalt
nickel
synthesis
affinity
Boranes
Ligands
dihydrides
ligands
boranes
Coordination Complexes
Hydrogen storage
products
regeneration
Ammonia
acetonitrile
Transition metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Mock, M. T., Potter, R. G., O'Hagan, M. J., Camaioni, D. M., Dougherty, W. G., Kassel, W. S., & DuBois, D. L. (2011). Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds. Inorganic Chemistry, 50(23), 11914-11928. https://doi.org/10.1021/ic200857x

Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds. / Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly J.; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. Scott; DuBois, Daniel L.

In: Inorganic Chemistry, Vol. 50, No. 23, 05.12.2011, p. 11914-11928.

Research output: Contribution to journalArticle

Mock, MT, Potter, RG, O'Hagan, MJ, Camaioni, DM, Dougherty, WG, Kassel, WS & DuBois, DL 2011, 'Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds', Inorganic Chemistry, vol. 50, no. 23, pp. 11914-11928. https://doi.org/10.1021/ic200857x
Mock MT, Potter RG, O'Hagan MJ, Camaioni DM, Dougherty WG, Kassel WS et al. Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds. Inorganic Chemistry. 2011 Dec 5;50(23):11914-11928. https://doi.org/10.1021/ic200857x
Mock, Michael T. ; Potter, Robert G. ; O'Hagan, Molly J. ; Camaioni, Donald M. ; Dougherty, William G. ; Kassel, W. Scott ; DuBois, Daniel L. / Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 23. pp. 11914-11928.
@article{95b41252f9b8473e808b04039a8f083a,
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 H2 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)2 (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX3 compounds having a hydride affinity (HA) greater than or equal to the HA of BEt3. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)2 and [HNi(dmpe)2]+, to form B-H bonds. The hydride donor abilities (ΔGH-°) of HCo(dmpe)2 and [HNi(dmpe)2]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX3 compounds. The collective data guided our selection of BX3 compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)2 was observed to transfer H- to BX3 compounds with X = H, OC6F5, and SPh. The reaction with B(SPh)3 is accompanied by the formation of dmpe-(BH3)2 and dmpe-(BH2(SPh))2 products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)2 and B(SPh)3 in the presence of triethylamine result in the formation of Et3N-BH2SPh and Et 3N-BH3 with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)2]+ with B(SPh)3 under analogous conditions give Et3N-BH2SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)2(SPh)] +. The synthesis and characterization of HCo(dedpe)2 (dedpe = Et2PCH2CH2PPh2) from H 2 and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)2Co(dedpe) 2][BF4].",
author = "Mock, {Michael T.} and Potter, {Robert G.} and O'Hagan, {Molly J.} and Camaioni, {Donald M.} and Dougherty, {William G.} and Kassel, {W. Scott} and DuBois, {Daniel L}",
year = "2011",
month = "12",
day = "5",
doi = "10.1021/ic200857x",
language = "English",
volume = "50",
pages = "11914--11928",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "23",

}

TY - JOUR

T1 - Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds

AU - Mock, Michael T.

AU - Potter, Robert G.

AU - O'Hagan, Molly J.

AU - Camaioni, Donald M.

AU - Dougherty, William G.

AU - Kassel, W. Scott

AU - DuBois, Daniel L

PY - 2011/12/5

Y1 - 2011/12/5

N2 - Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H2 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)2 (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX3 compounds having a hydride affinity (HA) greater than or equal to the HA of BEt3. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)2 and [HNi(dmpe)2]+, to form B-H bonds. The hydride donor abilities (ΔGH-°) of HCo(dmpe)2 and [HNi(dmpe)2]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX3 compounds. The collective data guided our selection of BX3 compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)2 was observed to transfer H- to BX3 compounds with X = H, OC6F5, and SPh. The reaction with B(SPh)3 is accompanied by the formation of dmpe-(BH3)2 and dmpe-(BH2(SPh))2 products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)2 and B(SPh)3 in the presence of triethylamine result in the formation of Et3N-BH2SPh and Et 3N-BH3 with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)2]+ with B(SPh)3 under analogous conditions give Et3N-BH2SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)2(SPh)] +. The synthesis and characterization of HCo(dedpe)2 (dedpe = Et2PCH2CH2PPh2) from H 2 and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)2Co(dedpe) 2][BF4].

AB - Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H2 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)2 (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX3 compounds having a hydride affinity (HA) greater than or equal to the HA of BEt3. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)2 and [HNi(dmpe)2]+, to form B-H bonds. The hydride donor abilities (ΔGH-°) of HCo(dmpe)2 and [HNi(dmpe)2]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX3 compounds. The collective data guided our selection of BX3 compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)2 was observed to transfer H- to BX3 compounds with X = H, OC6F5, and SPh. The reaction with B(SPh)3 is accompanied by the formation of dmpe-(BH3)2 and dmpe-(BH2(SPh))2 products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)2 and B(SPh)3 in the presence of triethylamine result in the formation of Et3N-BH2SPh and Et 3N-BH3 with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)2]+ with B(SPh)3 under analogous conditions give Et3N-BH2SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)2(SPh)] +. The synthesis and characterization of HCo(dedpe)2 (dedpe = Et2PCH2CH2PPh2) from H 2 and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)2Co(dedpe) 2][BF4].

UR - http://www.scopus.com/inward/record.url?scp=82355187830&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=82355187830&partnerID=8YFLogxK

U2 - 10.1021/ic200857x

DO - 10.1021/ic200857x

M3 - Article

C2 - 22040085

AN - SCOPUS:82355187830

VL - 50

SP - 11914

EP - 11928

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 23

ER -