Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}

Md Jakir Hossain; Subas Rajbangshi; Md Mehedi M. Khan; Shishir Ghosh; Graeme Hogarth; Edward Rosenberg; Kenneth I. Hardcastle; Michael G. Richmond; Shariff E. Kabir

doi:10.1016/j.jorganchem.2014.05.040

Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}

Md Jakir Hossain, Subas Rajbangshi, Md Mehedi M. Khan, Shishir Ghosh, Graeme Hogarth, Edward Rosenberg, Kenneth I. Hardcastle, Michael G. Richmond, Shariff E. Kabir^*

^*Corresponding author for this work

Chemistry

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Abstract

Reactions of Ru-3(CO)(10)(mu-dppf) (1) (dppf - 1,1'-bis(diphenylphosphino) ferrocene), Ru-3(CO)(10)(mu-dppm) (2) (dppm = bis(diphenylphosphino)methane), and the orthometalated derivative Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)} (3) with silanes (Ph3SiH, Et3SiH, Ph2SiH2) are reported. Treatment of 1 with Ph3SiH and Ph2SiH2 at room temperature leads to facile Si-H bond activation to afford Ru-3(CO)(9)(mu-dppf)(SiPh3)(mu-H) (4) (60% yield) and Ru-3(CO)(9)(mu-dppf)(SiPh2H)(mu-H) (6) (53% yield), respectively. The reaction of 1 with Ph3SiH has been investigated by electronic structure calculations, and these data have facilitated the analysis of the potential energy surface leading to 4. Compound 1 does not react with Et3SiH at room temperature but reacts at 68 degrees C to give Ru-3(CO)(9)(mu-dppf)(SiEt3)(mu-H) (5) in 45% yield. Reaction of 2 with Ph3SiH at room temperature yields two new products: Ru-3(CO)(9)(mu-dppm)(SiPh3)(mu-H) (7) in 40% yield and Ru-3(CO)(6)(mu(3)-O)(mu-dppm)(SiPh3)(mu-H) 3 (8) in 15% yield. Interestingly, at room temperature compound 7 slowly reverts back to 2 in solution with decomposition and liberation of Ph3SiH. Complex 8 can also be prepared from the direct reaction between 7 and H2O. Similar reactions of 2 with Et3SiH and Ph2SiH2 give only intractable materials. The orthometalated compound 3 does not react with Ph3SiH, Et3SiH and Ph2SiH2 at room temperature but does react at 66 degrees C to give Ru-3(mu-CO)(CO)(7){mu(3)-PPhCH2PPh( C6H4)}(SiR2R1)(mu-H)](9, R = R' = Ph, 71% yield; 10, R = R' = Et, 60% yield; 11, R = Ph, R' = H, 66% yield) by activation of the Si-H bond. Compounds 4 and 8-11 have been structurally characterized. In 4, both the dppf and the hydride bridge a common Ru-Ru vector, whereas NMR studies on 7 indicate that two ligands span different Ru-Ru edges. Compound 8 contains a face-capping oxo moiety, a terminally coordinated SiPh3 ligand, and three bridging hydride ligands, whereas 9-11 represent simple oxidative addition products. In all of the compounds examined, the triruthenium framework retains its integrity and the silyl groups occupy equatorial sites.

Original language	English
Pages (from-to)	185-195
Number of pages	11
Journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume	767
DOIs	https://doi.org/10.1016/j.jorganchem.2014.05.040
Publication status	Published - 15 Sept 2014

Keywords

Ruthenium carbonyl
Diphosphine
Silanes
Oxo-capped
Oxidative-addition
X-ray structures
OXIDATIVE ADDITION
CRYSTAL-STRUCTURE
CATALYTIC HYDROSILYLATION
CARBONYL CLUSTERS
METAL CLUSTER
COMPLEXES
RUTHENIUM
TRIOSMIUM
LIGANDS
1,1'-BIS(DIPHENYLPHOSPHINO)FERROCENE

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10.1016/j.jorganchem.2014.05.040

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Hossain, M. J., Rajbangshi, S., Khan, M. M. M., Ghosh, S., Hogarth, G., Rosenberg, E., Hardcastle, K. I., Richmond, M. G., & Kabir, S. E. (2014). Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 767, 185-195. https://doi.org/10.1016/j.jorganchem.2014.05.040

@article{47d886715f154a0fa8ccfb52044cc7a4,

title = "Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}",

abstract = "Reactions of Ru-3(CO)(10)(mu-dppf) (1) (dppf - 1,1'-bis(diphenylphosphino) ferrocene), Ru-3(CO)(10)(mu-dppm) (2) (dppm = bis(diphenylphosphino)methane), and the orthometalated derivative Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)} (3) with silanes (Ph3SiH, Et3SiH, Ph2SiH2) are reported. Treatment of 1 with Ph3SiH and Ph2SiH2 at room temperature leads to facile Si-H bond activation to afford Ru-3(CO)(9)(mu-dppf)(SiPh3)(mu-H) (4) (60% yield) and Ru-3(CO)(9)(mu-dppf)(SiPh2H)(mu-H) (6) (53% yield), respectively. The reaction of 1 with Ph3SiH has been investigated by electronic structure calculations, and these data have facilitated the analysis of the potential energy surface leading to 4. Compound 1 does not react with Et3SiH at room temperature but reacts at 68 degrees C to give Ru-3(CO)(9)(mu-dppf)(SiEt3)(mu-H) (5) in 45% yield. Reaction of 2 with Ph3SiH at room temperature yields two new products: Ru-3(CO)(9)(mu-dppm)(SiPh3)(mu-H) (7) in 40% yield and Ru-3(CO)(6)(mu(3)-O)(mu-dppm)(SiPh3)(mu-H) 3 (8) in 15% yield. Interestingly, at room temperature compound 7 slowly reverts back to 2 in solution with decomposition and liberation of Ph3SiH. Complex 8 can also be prepared from the direct reaction between 7 and H2O. Similar reactions of 2 with Et3SiH and Ph2SiH2 give only intractable materials. The orthometalated compound 3 does not react with Ph3SiH, Et3SiH and Ph2SiH2 at room temperature but does react at 66 degrees C to give Ru-3(mu-CO)(CO)(7){mu(3)-PPhCH2PPh( C6H4)}(SiR2R1)(mu-H)](9, R = R' = Ph, 71% yield; 10, R = R' = Et, 60% yield; 11, R = Ph, R' = H, 66% yield) by activation of the Si-H bond. Compounds 4 and 8-11 have been structurally characterized. In 4, both the dppf and the hydride bridge a common Ru-Ru vector, whereas NMR studies on 7 indicate that two ligands span different Ru-Ru edges. Compound 8 contains a face-capping oxo moiety, a terminally coordinated SiPh3 ligand, and three bridging hydride ligands, whereas 9-11 represent simple oxidative addition products. In all of the compounds examined, the triruthenium framework retains its integrity and the silyl groups occupy equatorial sites. ",

keywords = "Ruthenium carbonyl, Diphosphine, Silanes, Oxo-capped, Oxidative-addition, X-ray structures, OXIDATIVE ADDITION, CRYSTAL-STRUCTURE, CATALYTIC HYDROSILYLATION, CARBONYL CLUSTERS, METAL CLUSTER, COMPLEXES, RUTHENIUM, TRIOSMIUM, LIGANDS, 1,1'-BIS(DIPHENYLPHOSPHINO)FERROCENE",

author = "Hossain, {Md Jakir} and Subas Rajbangshi and Khan, {Md Mehedi M.} and Shishir Ghosh and Graeme Hogarth and Edward Rosenberg and Hardcastle, {Kenneth I.} and Richmond, {Michael G.} and Kabir, {Shariff E.}",

year = "2014",

month = sep,

day = "15",

doi = "10.1016/j.jorganchem.2014.05.040",

language = "English",

volume = "767",

pages = "185--195",

journal = "JOURNAL OF ORGANOMETALLIC CHEMISTRY",

issn = "0022-328X",

publisher = "Elsevier",

}

Hossain, MJ, Rajbangshi, S, Khan, MMM, Ghosh, S, Hogarth, G, Rosenberg, E, Hardcastle, KI, Richmond, MG & Kabir, SE 2014, 'Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}', JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 767, pp. 185-195. https://doi.org/10.1016/j.jorganchem.2014.05.040

Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}. / Hossain, Md Jakir; Rajbangshi, Subas; Khan, Md Mehedi M. et al.
In: JOURNAL OF ORGANOMETALLIC CHEMISTRY, Vol. 767, 15.09.2014, p. 185-195.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}

AU - Hossain, Md Jakir

AU - Rajbangshi, Subas

AU - Khan, Md Mehedi M.

AU - Ghosh, Shishir

AU - Hogarth, Graeme

AU - Rosenberg, Edward

AU - Hardcastle, Kenneth I.

AU - Richmond, Michael G.

AU - Kabir, Shariff E.

PY - 2014/9/15

Y1 - 2014/9/15

N2 - Reactions of Ru-3(CO)(10)(mu-dppf) (1) (dppf - 1,1'-bis(diphenylphosphino) ferrocene), Ru-3(CO)(10)(mu-dppm) (2) (dppm = bis(diphenylphosphino)methane), and the orthometalated derivative Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)} (3) with silanes (Ph3SiH, Et3SiH, Ph2SiH2) are reported. Treatment of 1 with Ph3SiH and Ph2SiH2 at room temperature leads to facile Si-H bond activation to afford Ru-3(CO)(9)(mu-dppf)(SiPh3)(mu-H) (4) (60% yield) and Ru-3(CO)(9)(mu-dppf)(SiPh2H)(mu-H) (6) (53% yield), respectively. The reaction of 1 with Ph3SiH has been investigated by electronic structure calculations, and these data have facilitated the analysis of the potential energy surface leading to 4. Compound 1 does not react with Et3SiH at room temperature but reacts at 68 degrees C to give Ru-3(CO)(9)(mu-dppf)(SiEt3)(mu-H) (5) in 45% yield. Reaction of 2 with Ph3SiH at room temperature yields two new products: Ru-3(CO)(9)(mu-dppm)(SiPh3)(mu-H) (7) in 40% yield and Ru-3(CO)(6)(mu(3)-O)(mu-dppm)(SiPh3)(mu-H) 3 (8) in 15% yield. Interestingly, at room temperature compound 7 slowly reverts back to 2 in solution with decomposition and liberation of Ph3SiH. Complex 8 can also be prepared from the direct reaction between 7 and H2O. Similar reactions of 2 with Et3SiH and Ph2SiH2 give only intractable materials. The orthometalated compound 3 does not react with Ph3SiH, Et3SiH and Ph2SiH2 at room temperature but does react at 66 degrees C to give Ru-3(mu-CO)(CO)(7){mu(3)-PPhCH2PPh( C6H4)}(SiR2R1)(mu-H)](9, R = R' = Ph, 71% yield; 10, R = R' = Et, 60% yield; 11, R = Ph, R' = H, 66% yield) by activation of the Si-H bond. Compounds 4 and 8-11 have been structurally characterized. In 4, both the dppf and the hydride bridge a common Ru-Ru vector, whereas NMR studies on 7 indicate that two ligands span different Ru-Ru edges. Compound 8 contains a face-capping oxo moiety, a terminally coordinated SiPh3 ligand, and three bridging hydride ligands, whereas 9-11 represent simple oxidative addition products. In all of the compounds examined, the triruthenium framework retains its integrity and the silyl groups occupy equatorial sites.

AB - Reactions of Ru-3(CO)(10)(mu-dppf) (1) (dppf - 1,1'-bis(diphenylphosphino) ferrocene), Ru-3(CO)(10)(mu-dppm) (2) (dppm = bis(diphenylphosphino)methane), and the orthometalated derivative Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)} (3) with silanes (Ph3SiH, Et3SiH, Ph2SiH2) are reported. Treatment of 1 with Ph3SiH and Ph2SiH2 at room temperature leads to facile Si-H bond activation to afford Ru-3(CO)(9)(mu-dppf)(SiPh3)(mu-H) (4) (60% yield) and Ru-3(CO)(9)(mu-dppf)(SiPh2H)(mu-H) (6) (53% yield), respectively. The reaction of 1 with Ph3SiH has been investigated by electronic structure calculations, and these data have facilitated the analysis of the potential energy surface leading to 4. Compound 1 does not react with Et3SiH at room temperature but reacts at 68 degrees C to give Ru-3(CO)(9)(mu-dppf)(SiEt3)(mu-H) (5) in 45% yield. Reaction of 2 with Ph3SiH at room temperature yields two new products: Ru-3(CO)(9)(mu-dppm)(SiPh3)(mu-H) (7) in 40% yield and Ru-3(CO)(6)(mu(3)-O)(mu-dppm)(SiPh3)(mu-H) 3 (8) in 15% yield. Interestingly, at room temperature compound 7 slowly reverts back to 2 in solution with decomposition and liberation of Ph3SiH. Complex 8 can also be prepared from the direct reaction between 7 and H2O. Similar reactions of 2 with Et3SiH and Ph2SiH2 give only intractable materials. The orthometalated compound 3 does not react with Ph3SiH, Et3SiH and Ph2SiH2 at room temperature but does react at 66 degrees C to give Ru-3(mu-CO)(CO)(7){mu(3)-PPhCH2PPh( C6H4)}(SiR2R1)(mu-H)](9, R = R' = Ph, 71% yield; 10, R = R' = Et, 60% yield; 11, R = Ph, R' = H, 66% yield) by activation of the Si-H bond. Compounds 4 and 8-11 have been structurally characterized. In 4, both the dppf and the hydride bridge a common Ru-Ru vector, whereas NMR studies on 7 indicate that two ligands span different Ru-Ru edges. Compound 8 contains a face-capping oxo moiety, a terminally coordinated SiPh3 ligand, and three bridging hydride ligands, whereas 9-11 represent simple oxidative addition products. In all of the compounds examined, the triruthenium framework retains its integrity and the silyl groups occupy equatorial sites.

KW - Ruthenium carbonyl

KW - Diphosphine

KW - Silanes

KW - Oxo-capped

KW - Oxidative-addition

KW - X-ray structures

KW - OXIDATIVE ADDITION

KW - CRYSTAL-STRUCTURE

KW - CATALYTIC HYDROSILYLATION

KW - CARBONYL CLUSTERS

KW - METAL CLUSTER

KW - COMPLEXES

KW - RUTHENIUM

KW - TRIOSMIUM

KW - LIGANDS

KW - 1,1'-BIS(DIPHENYLPHOSPHINO)FERROCENE

U2 - 10.1016/j.jorganchem.2014.05.040

DO - 10.1016/j.jorganchem.2014.05.040

M3 - Article

SN - 0022-328X

VL - 767

SP - 185

EP - 195

JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

ER -

Hossain MJ, Rajbangshi S, Khan MMM, Ghosh S, Hogarth G, Rosenberg E et al. Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 2014 Sept 15;767:185-195. doi: 10.1016/j.jorganchem.2014.05.040

Experimental and computational studies on the reaction of silanes with the diphosphine-bridged triruthenium clusters Ru-3(CO)(10)(mu-dppf), Ru-3(CO)(10)(mu-dppm) and Ru-3(CO)(9){mu(3)-PPhCH2PPh(C6H4)}

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