Oxidative-addition of the N-H bond of saccharin (sacH) to a triosmium centre: Synthesis, structure and reactivity of Os3(CO)10(μ-H)(μ-sac)

Shirajum Monira; Sadiya Afrin; Kazi A. Azam; Md Kamal Hossain; Derek A. Tocher; Shishir Ghosh; Subas Rajbangshi; Shariff E. Kabir; Graeme Hogarth

doi:10.1016/j.jorganchem.2015.09.032

Oxidative-addition of the N-H bond of saccharin (sacH) to a triosmium centre: Synthesis, structure and reactivity of Os₃(CO)₁₀(μ-H)(μ-sac)

Shirajum Monira, Sadiya Afrin, Kazi A. Azam^*, Md Kamal Hossain, Derek A. Tocher, Shishir Ghosh, Subas Rajbangshi, Shariff E. Kabir, Graeme Hogarth

^*Corresponding author for this work

Chemistry

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Abstract

Saccharin (sacH) is a widely-used sweetener and consequently its chemistry has been extensively studied, but here we report a rare example of its reactivity towards a multinuclear metal centre. Lightly-stabilized Os₃(CO)_10-n(NCMe)_n (n = 1, 2) react with sacH to afford Os₃(CO)₁₀(μ-H) (μ-sac) (1) in which the sac ligand bridges an osmium-osmium vector via nitrogen and the carbonylic oxygen (μ-N,O). The reactivity of 1 towards monodentate phosphines, PR₃ (R = Ph, Th, Fu), has been investigated. Carbonyl substitution affords both mono- and bis-phosphine substituted derivatives Os₃(CO)₉(PR₃) (μ-H) (μ-sac) (2) and Os₃(CO)₈(PR₃)₂(μ-H) (μ-sac) (3) respectively. In the mono-substituted derivatives, the phosphine occupies an equatorial position on the osmium that is directly bonded to the carbonylic oxygen of saccharinate, while in the bis-(phosphine) substituted derivatives the second phosphine is bound to the remote osmium also occupying an equatorial site. In all complexes the saccharinate ligand remains in the bidentate N,O coordination mode thus playing a directing spectator role in these reactions.

Original language	English
Pages (from-to)	281-290
Number of pages	10
Journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume	799-800
Early online date	9 Oct 2015
DOIs	https://doi.org/10.1016/j.jorganchem.2015.09.032
Publication status	Published - 15 Dec 2015

Keywords

Carbonyls
N-H bond activation
Saccharin
Triosmium clusters
X-ray structures

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10.1016/j.jorganchem.2015.09.032

Oxidative-addition of the_MONIRA_Accepted24September2015_GREEN AAMAccepted author manuscript, 1.12 MBLicence: CC BY-NC-ND

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Monira, S., Afrin, S., Azam, K. A., Hossain, M. K., Tocher, D. A., Ghosh, S., Rajbangshi, S., Kabir, S. E., & Hogarth, G. (2015). Oxidative-addition of the N-H bond of saccharin (sacH) to a triosmium centre: Synthesis, structure and reactivity of Os₃(CO)₁₀(μ-H)(μ-sac) . JOURNAL OF ORGANOMETALLIC CHEMISTRY, 799-800, 281-290. https://doi.org/10.1016/j.jorganchem.2015.09.032

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title = "Oxidative-addition of the N-H bond of saccharin (sacH) to a triosmium centre: Synthesis, structure and reactivity of Os3(CO)10(μ-H)(μ-sac) ",

abstract = "Saccharin (sacH) is a widely-used sweetener and consequently its chemistry has been extensively studied, but here we report a rare example of its reactivity towards a multinuclear metal centre. Lightly-stabilized Os3(CO)10-n(NCMe)n (n = 1, 2) react with sacH to afford Os3(CO)10(μ-H) (μ-sac) (1) in which the sac ligand bridges an osmium-osmium vector via nitrogen and the carbonylic oxygen (μ-N,O). The reactivity of 1 towards monodentate phosphines, PR3 (R = Ph, Th, Fu), has been investigated. Carbonyl substitution affords both mono- and bis-phosphine substituted derivatives Os3(CO)9(PR3) (μ-H) (μ-sac) (2) and Os3(CO)8(PR3)2(μ-H) (μ-sac) (3) respectively. In the mono-substituted derivatives, the phosphine occupies an equatorial position on the osmium that is directly bonded to the carbonylic oxygen of saccharinate, while in the bis-(phosphine) substituted derivatives the second phosphine is bound to the remote osmium also occupying an equatorial site. In all complexes the saccharinate ligand remains in the bidentate N,O coordination mode thus playing a directing spectator role in these reactions.",

keywords = "Carbonyls, N-H bond activation, Saccharin, Triosmium clusters, X-ray structures",

author = "Shirajum Monira and Sadiya Afrin and Azam, {Kazi A.} and Hossain, {Md Kamal} and Tocher, {Derek A.} and Shishir Ghosh and Subas Rajbangshi and Kabir, {Shariff E.} and Graeme Hogarth",

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doi = "10.1016/j.jorganchem.2015.09.032",

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T1 - Oxidative-addition of the N-H bond of saccharin (sacH) to a triosmium centre

T2 - Synthesis, structure and reactivity of Os3(CO)10(μ-H)(μ-sac)

AU - Monira, Shirajum

AU - Afrin, Sadiya

AU - Azam, Kazi A.

AU - Hossain, Md Kamal

AU - Tocher, Derek A.

AU - Ghosh, Shishir

AU - Rajbangshi, Subas

AU - Kabir, Shariff E.

AU - Hogarth, Graeme

PY - 2015/12/15

Y1 - 2015/12/15

N2 - Saccharin (sacH) is a widely-used sweetener and consequently its chemistry has been extensively studied, but here we report a rare example of its reactivity towards a multinuclear metal centre. Lightly-stabilized Os3(CO)10-n(NCMe)n (n = 1, 2) react with sacH to afford Os3(CO)10(μ-H) (μ-sac) (1) in which the sac ligand bridges an osmium-osmium vector via nitrogen and the carbonylic oxygen (μ-N,O). The reactivity of 1 towards monodentate phosphines, PR3 (R = Ph, Th, Fu), has been investigated. Carbonyl substitution affords both mono- and bis-phosphine substituted derivatives Os3(CO)9(PR3) (μ-H) (μ-sac) (2) and Os3(CO)8(PR3)2(μ-H) (μ-sac) (3) respectively. In the mono-substituted derivatives, the phosphine occupies an equatorial position on the osmium that is directly bonded to the carbonylic oxygen of saccharinate, while in the bis-(phosphine) substituted derivatives the second phosphine is bound to the remote osmium also occupying an equatorial site. In all complexes the saccharinate ligand remains in the bidentate N,O coordination mode thus playing a directing spectator role in these reactions.

AB - Saccharin (sacH) is a widely-used sweetener and consequently its chemistry has been extensively studied, but here we report a rare example of its reactivity towards a multinuclear metal centre. Lightly-stabilized Os3(CO)10-n(NCMe)n (n = 1, 2) react with sacH to afford Os3(CO)10(μ-H) (μ-sac) (1) in which the sac ligand bridges an osmium-osmium vector via nitrogen and the carbonylic oxygen (μ-N,O). The reactivity of 1 towards monodentate phosphines, PR3 (R = Ph, Th, Fu), has been investigated. Carbonyl substitution affords both mono- and bis-phosphine substituted derivatives Os3(CO)9(PR3) (μ-H) (μ-sac) (2) and Os3(CO)8(PR3)2(μ-H) (μ-sac) (3) respectively. In the mono-substituted derivatives, the phosphine occupies an equatorial position on the osmium that is directly bonded to the carbonylic oxygen of saccharinate, while in the bis-(phosphine) substituted derivatives the second phosphine is bound to the remote osmium also occupying an equatorial site. In all complexes the saccharinate ligand remains in the bidentate N,O coordination mode thus playing a directing spectator role in these reactions.

KW - Carbonyls

KW - N-H bond activation

KW - Saccharin

KW - Triosmium clusters

KW - X-ray structures

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U2 - 10.1016/j.jorganchem.2015.09.032

DO - 10.1016/j.jorganchem.2015.09.032

M3 - Article

AN - SCOPUS:84944790500

SN - 0022-328X

VL - 799-800

SP - 281

EP - 290

JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

ER -

Oxidative-addition of the N-H bond of saccharin (sacH) to a triosmium centre: Synthesis, structure and reactivity of Os₃(CO)₁₀(μ-H)(μ-sac)

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