Binuclear (salen)osmium phosphinidine and phosphiniminato complexes

Gui Chen; Wai Lun Man; Shek Man Yiu; Tsz Wing Wong; Lap Szeto; Wing Tak Wong; Tai Chu Lau

doi:10.1039/c0dt01367f

Binuclear (salen)osmium phosphinidine and phosphiniminato complexes

Gui Chen, Wai Lun Man, Shek Man Yiu, Tsz Wing Wong, Lap Szeto, Wing Tak Wong, Tai Chu Lau^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

13 Citations (Scopus)

Abstract

The preparation of a number of binuclear (salen)osmium phosphinidine and phosphiniminato complexes using various strategies are described. Treatment of [Os^VI(N)(L¹)(sol)](X) (sol = H₂O or MeOH) with PPh₃ affords an osmium(iv) phosphinidine complex [Os ^IV{N(H)PPh₃}(L¹)(OMe)](X) (X = PF ₆1a, ClO₄1b). If the reaction is carried out in CH ₂Cl₂ in the presence of excess pyrazine the osmium(iii) phosphinidine species [Os^III{N(H)PPh₃}(L ¹)(pz)](PF₆) 2 can be generated. On the other hand, if the reaction is carried out in CH₂Cl₂ in the presence of a small amount of H₂O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L¹){PPh₃N(H)}Os^IV-O-Os ^IV{N(H)PPh₃}(L¹)](PF₆)₂3. Furthermore, if the reaction of [Os^VI(N)(L¹)(OH ₂)]PF₆ with PPh₃ is done in the presence of 2, the μ-pyrazine species, [(L¹){PPh₃N(H)}Os ^III-pz-Os^III{N(H)PPh₃}(L¹)](PF ₆)₂4 can be isolated. Novel binuclear osmium(iv) complexes can be prepared by the use of a diphosphine ligand to attack two Os ^VIN. Reaction of [Os^VI(N)(L¹)(OH ₂)](PF₆) with PPh₂-CC-PPh₂ or PPh₂-(CH₂)₃-PPh₂ in MeOH affords the binuclear complexes [(MeO)(L¹)Os^IV{N(H)PPh ₂-R-PPh₂N(H)}Os^IV(L¹)(OMe)](PF ₆)₂ (R = CC 5, (CH₂)₃6). Reaction of [Os^VI(N)(L²)Cl] with PPh₂FcPPh₂ generates a novel trimetallic complex, [Cl(L²)Os ^IV{NPPh₂-Fc-PPh₂N}Os^IV(L ²)Cl] 7. The structures of 1b, 2, 3, 4, 5 and 7 have been determined by X-ray crystallography.

Original language	English
Pages (from-to)	1938-1944
Number of pages	7
Journal	Dalton Transactions
Volume	40
Issue number	9
Early online date	26 Jan 2011
DOIs	https://doi.org/10.1039/c0dt01367f
Publication status	Published - 7 Mar 2011

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Inorganic Chemistry

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@article{4e1e0ee5f4c54be086e947ba133644b3,

title = "Binuclear (salen)osmium phosphinidine and phosphiniminato complexes",

abstract = "The preparation of a number of binuclear (salen)osmium phosphinidine and phosphiniminato complexes using various strategies are described. Treatment of [OsVI(N)(L1)(sol)](X) (sol = H2O or MeOH) with PPh3 affords an osmium(iv) phosphinidine complex [Os IV{N(H)PPh3}(L1)(OMe)](X) (X = PF 61a, ClO41b). If the reaction is carried out in CH 2Cl2 in the presence of excess pyrazine the osmium(iii) phosphinidine species [OsIII{N(H)PPh3}(L 1)(pz)](PF6) 2 can be generated. On the other hand, if the reaction is carried out in CH2Cl2 in the presence of a small amount of H2O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L1){PPh3N(H)}OsIV-O-Os IV{N(H)PPh3}(L1)](PF6)23. Furthermore, if the reaction of [OsVI(N)(L1)(OH 2)]PF6 with PPh3 is done in the presence of 2, the μ-pyrazine species, [(L1){PPh3N(H)}Os III-pz-OsIII{N(H)PPh3}(L1)](PF 6)24 can be isolated. Novel binuclear osmium(iv) complexes can be prepared by the use of a diphosphine ligand to attack two Os VIN. Reaction of [OsVI(N)(L1)(OH 2)](PF6) with PPh2-CC-PPh2 or PPh2-(CH2)3-PPh2 in MeOH affords the binuclear complexes [(MeO)(L1)OsIV{N(H)PPh 2-R-PPh2N(H)}OsIV(L1)(OMe)](PF 6)2 (R = CC 5, (CH2)36). Reaction of [OsVI(N)(L2)Cl] with PPh2FcPPh2 generates a novel trimetallic complex, [Cl(L2)Os IV{NPPh2-Fc-PPh2N}OsIV(L 2)Cl] 7. The structures of 1b, 2, 3, 4, 5 and 7 have been determined by X-ray crystallography.",

author = "Gui Chen and Man, {Wai Lun} and Yiu, {Shek Man} and Wong, {Tsz Wing} and Lap Szeto and Wong, {Wing Tak} and Lau, {Tai Chu}",

note = "This work was supported by the Area of Excellence Scheme, University Grants Committee, Hong Kong (AoE/P-03-08) and the Research Grants Council of Hong Kong (CityU 101607).",

year = "2011",

month = mar,

day = "7",

doi = "10.1039/c0dt01367f",

language = "English",

volume = "40",

pages = "1938--1944",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "9",

}

TY - JOUR

T1 - Binuclear (salen)osmium phosphinidine and phosphiniminato complexes

AU - Chen, Gui

AU - Man, Wai Lun

AU - Yiu, Shek Man

AU - Wong, Tsz Wing

AU - Szeto, Lap

AU - Wong, Wing Tak

AU - Lau, Tai Chu

N1 - This work was supported by the Area of Excellence Scheme, University Grants Committee, Hong Kong (AoE/P-03-08) and the Research Grants Council of Hong Kong (CityU 101607).

PY - 2011/3/7

Y1 - 2011/3/7

N2 - The preparation of a number of binuclear (salen)osmium phosphinidine and phosphiniminato complexes using various strategies are described. Treatment of [OsVI(N)(L1)(sol)](X) (sol = H2O or MeOH) with PPh3 affords an osmium(iv) phosphinidine complex [Os IV{N(H)PPh3}(L1)(OMe)](X) (X = PF 61a, ClO41b). If the reaction is carried out in CH 2Cl2 in the presence of excess pyrazine the osmium(iii) phosphinidine species [OsIII{N(H)PPh3}(L 1)(pz)](PF6) 2 can be generated. On the other hand, if the reaction is carried out in CH2Cl2 in the presence of a small amount of H2O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L1){PPh3N(H)}OsIV-O-Os IV{N(H)PPh3}(L1)](PF6)23. Furthermore, if the reaction of [OsVI(N)(L1)(OH 2)]PF6 with PPh3 is done in the presence of 2, the μ-pyrazine species, [(L1){PPh3N(H)}Os III-pz-OsIII{N(H)PPh3}(L1)](PF 6)24 can be isolated. Novel binuclear osmium(iv) complexes can be prepared by the use of a diphosphine ligand to attack two Os VIN. Reaction of [OsVI(N)(L1)(OH 2)](PF6) with PPh2-CC-PPh2 or PPh2-(CH2)3-PPh2 in MeOH affords the binuclear complexes [(MeO)(L1)OsIV{N(H)PPh 2-R-PPh2N(H)}OsIV(L1)(OMe)](PF 6)2 (R = CC 5, (CH2)36). Reaction of [OsVI(N)(L2)Cl] with PPh2FcPPh2 generates a novel trimetallic complex, [Cl(L2)Os IV{NPPh2-Fc-PPh2N}OsIV(L 2)Cl] 7. The structures of 1b, 2, 3, 4, 5 and 7 have been determined by X-ray crystallography.

AB - The preparation of a number of binuclear (salen)osmium phosphinidine and phosphiniminato complexes using various strategies are described. Treatment of [OsVI(N)(L1)(sol)](X) (sol = H2O or MeOH) with PPh3 affords an osmium(iv) phosphinidine complex [Os IV{N(H)PPh3}(L1)(OMe)](X) (X = PF 61a, ClO41b). If the reaction is carried out in CH 2Cl2 in the presence of excess pyrazine the osmium(iii) phosphinidine species [OsIII{N(H)PPh3}(L 1)(pz)](PF6) 2 can be generated. On the other hand, if the reaction is carried out in CH2Cl2 in the presence of a small amount of H2O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L1){PPh3N(H)}OsIV-O-Os IV{N(H)PPh3}(L1)](PF6)23. Furthermore, if the reaction of [OsVI(N)(L1)(OH 2)]PF6 with PPh3 is done in the presence of 2, the μ-pyrazine species, [(L1){PPh3N(H)}Os III-pz-OsIII{N(H)PPh3}(L1)](PF 6)24 can be isolated. Novel binuclear osmium(iv) complexes can be prepared by the use of a diphosphine ligand to attack two Os VIN. Reaction of [OsVI(N)(L1)(OH 2)](PF6) with PPh2-CC-PPh2 or PPh2-(CH2)3-PPh2 in MeOH affords the binuclear complexes [(MeO)(L1)OsIV{N(H)PPh 2-R-PPh2N(H)}OsIV(L1)(OMe)](PF 6)2 (R = CC 5, (CH2)36). Reaction of [OsVI(N)(L2)Cl] with PPh2FcPPh2 generates a novel trimetallic complex, [Cl(L2)Os IV{NPPh2-Fc-PPh2N}OsIV(L 2)Cl] 7. The structures of 1b, 2, 3, 4, 5 and 7 have been determined by X-ray crystallography.

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U2 - 10.1039/c0dt01367f

DO - 10.1039/c0dt01367f

M3 - Journal article

AN - SCOPUS:79951597940

SN - 1477-9226

VL - 40

SP - 1938

EP - 1944

JO - Dalton Transactions

JF - Dalton Transactions

IS - 9

ER -

Binuclear (salen)osmium phosphinidine and phosphiniminato complexes

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