Photochemical oxidative addition of germane and diphenylgermane to ruthenium dihydride complexes

TY - JOUR

T1 - Photochemical oxidative addition of germane and diphenylgermane to ruthenium dihydride complexes

AU - Dickinson, David P.

AU - Evans, Simon W.

AU - Grellier, Mary

AU - Kendall, Hannah

AU - Perutz, Robin Noel

AU - Procacci, Barbara

AU - Sabo-Etienne, Sylviane

AU - Smart, Katharine A.

AU - Whitwood, Adrian C.

N1 - © 2019 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2019/2/11

Y1 - 2019/2/11

N2 - Photochemical reactions of germane and diphenylgermane with Ru(PP) 2 H 2 (PP = R 2 PCH 2 CH 2 PR 2 or DuPhos, R = Ph dppe, R = Et depe, R = Me dmpe) are reported. Reaction with GeH 4 generates a mixture of cis and trans isomers of Ru(PP) 2 (GeH 3 )H except for the DuPhos complex which yields the product only in the cis form. In situ laser photolysis (355 nm) demonstrates that the initial product is the cis isomer that undergoes thermal isomerization to the trans isomer. The complex cis-[Ru(dppe) 2 (GeH 3 )H] crystallizes selectively, allowing determination of its X-ray structure as a germyl hydride with a long Ru-H···Ge separation of 2.64(3) Å indicating that no residual interaction between the RuH and Ge is present. DFT calculations are also consistent with full oxidative addition. The structure of cis-[Ru(DuPhos) 2 (GeH 3 )H] reveals significant distortion from an octahedral geometry. The major species in the crystal (95%) exhibits a structure with a Ru-H···Ge distance of 2.42(5) Å suggesting negligible interaction between these centers. DFT calculations of the structure are consistent with the experimental determination. The reactions of Ru(PP) 2 H 2 with diphenylgermane yield cis-[Ru(PP) 2 (GePh 2 H)H] exclusively for PP = dmpe and depe, while the cis isomer is dominant in the case of dppe. A photochemical competition reaction between Ru(dppe) 2 (H) 2 and the two substrates Ph 2 SiH 2 and Ph 2 GeH 2 results in both Si-H and Ge-H oxidative addition activation with a kinetic preference (0.18:1) for the germyl hydride product. Thermal conversion of Ru(dppe) 2 (SiPh 2 H)H to Ru(dppe) 2 (GePh 2 H)H is observed on heating.

AB - Photochemical reactions of germane and diphenylgermane with Ru(PP) 2 H 2 (PP = R 2 PCH 2 CH 2 PR 2 or DuPhos, R = Ph dppe, R = Et depe, R = Me dmpe) are reported. Reaction with GeH 4 generates a mixture of cis and trans isomers of Ru(PP) 2 (GeH 3 )H except for the DuPhos complex which yields the product only in the cis form. In situ laser photolysis (355 nm) demonstrates that the initial product is the cis isomer that undergoes thermal isomerization to the trans isomer. The complex cis-[Ru(dppe) 2 (GeH 3 )H] crystallizes selectively, allowing determination of its X-ray structure as a germyl hydride with a long Ru-H···Ge separation of 2.64(3) Å indicating that no residual interaction between the RuH and Ge is present. DFT calculations are also consistent with full oxidative addition. The structure of cis-[Ru(DuPhos) 2 (GeH 3 )H] reveals significant distortion from an octahedral geometry. The major species in the crystal (95%) exhibits a structure with a Ru-H···Ge distance of 2.42(5) Å suggesting negligible interaction between these centers. DFT calculations of the structure are consistent with the experimental determination. The reactions of Ru(PP) 2 H 2 with diphenylgermane yield cis-[Ru(PP) 2 (GePh 2 H)H] exclusively for PP = dmpe and depe, while the cis isomer is dominant in the case of dppe. A photochemical competition reaction between Ru(dppe) 2 (H) 2 and the two substrates Ph 2 SiH 2 and Ph 2 GeH 2 results in both Si-H and Ge-H oxidative addition activation with a kinetic preference (0.18:1) for the germyl hydride product. Thermal conversion of Ru(dppe) 2 (SiPh 2 H)H to Ru(dppe) 2 (GePh 2 H)H is observed on heating.

UR - http://www.scopus.com/inward/record.url?scp=85060829806&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.8b00770

DO - 10.1021/acs.organomet.8b00770

M3 - Article

AN - SCOPUS:85060829806

SN - 0276-7333

VL - 38

SP - 626

EP - 637

JO - Organometallics

JF - Organometallics

IS - 3

ER -