The versatile coordination modes of monophosphine-o-carborane in the formation of iridium and rhodium complexes: synthesis, reactivity, and characterization.
Chemistry. 2010 Oct 18; 16(39):12017-27.C

Abstract

Monophosphine-o-carborane has four competitive coordination modes when it coordinates to metal centers. To explore the structural transitions driven by these competitive coordination modes, a series of monophosphine-o-carborane Ir,Rh complexes were synthesized and characterized. [Cp*M(Cl)(2){1-(PPh(2))-1,2-C(2)B(10)H(11)}] (M=Ir (1a), Rh (1b); Cp*=η(5)-C(5)Me(5)), [Cp*Ir(H){7-(PPh(2))-7,8-C(2)B(9)H(11)}] (2a), and [1-(PPh(2))-3-(η(5)-Cp*)-3,1,2-MC(2)B(9)H(10)] (M=Ir (3a), Rh (3b)) can be all prepared directly by the reaction of 1-(PPh(2))-1,2-C(2)B(10)H(11) with dimeric complexes [(Cp*MCl(2))(2)] (M=Ir, Rh) under different conditions. Compound 3b was treated with AgOTf (OTf=CF(3)SO(3) (-)) to afford the tetranuclear metallacarborane [Ag(2)(thf)(2)(OTf)(2){1-(PPh(2))-3-(η(5)-Cp*)-3,1,2-RhC(2)B(9)H(10)}(2)] (4b). The arylphosphine group in 3a and 3b was functionalized by elemental sulfur (1 equiv) in the presence of Et(3)N to afford [1-{(S)PPh(2)}-3-(η(5)-Cp*)-3,1,2-MC(2)B(9)H(10)] (M=Ir (5a), Rh (5b)). Additionally, the 1-(PPh(2))-1,2-C(2)B(10)H(11) ligand was functionalized by elemental sulfur (2 equiv) and then treated with [(Cp*IrCl(2))(2)], thus resulting in two 16-electron complexes [Cp*Ir(7-{(S)PPh(2)}-8-S-7,8-C(2)B(9)H(9))] (6a) and [Cp*Ir(7-{(S)PPh(2)}-8-S-9-OCH(3)-7,8-C(2)B(9)H(9))] (7a). Compound 6a further reacted with nBuPPh(2), thereby leading to 18-electron complex [Cp*Ir(nBuPPh(2))(7-{(S)PPh(2)}-8-S-7,8-C(2)B(9)H(10))] (8a). The influences of other factors on structural transitions or the formation of targeted compounds, including reaction temperature and solvent, were also explored.

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Authors+Show Affiliations

Huo XK

Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, Shanghai 200433, P.R. China.

Su G

No affiliation info available

Jin GX

No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

20827699

Citation

Huo, Xian-Kuan, et al. "The Versatile Coordination Modes of Monophosphine-o-carborane in the Formation of Iridium and Rhodium Complexes: Synthesis, Reactivity, and Characterization." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 16, no. 39, 2010, pp. 12017-27.

Huo XK, Su G, Jin GX. The versatile coordination modes of monophosphine-o-carborane in the formation of iridium and rhodium complexes: synthesis, reactivity, and characterization. Chemistry. 2010;16(39):12017-27.

Huo, X. K., Su, G., & Jin, G. X. (2010). The versatile coordination modes of monophosphine-o-carborane in the formation of iridium and rhodium complexes: synthesis, reactivity, and characterization. Chemistry (Weinheim an Der Bergstrasse, Germany), 16(39), 12017-27. https://doi.org/10.1002/chem.201001278

Huo XK, Su G, Jin GX. The Versatile Coordination Modes of Monophosphine-o-carborane in the Formation of Iridium and Rhodium Complexes: Synthesis, Reactivity, and Characterization. Chemistry. 2010 Oct 18;16(39):12017-27. PubMed PMID: 20827699.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - The versatile coordination modes of monophosphine-o-carborane in the formation of iridium and rhodium complexes: synthesis, reactivity, and characterization. AU - Huo,Xian-Kuan, AU - Su,Ge, AU - Jin,Guo-Xin, PY - 2010/9/10/entrez PY - 2010/9/10/pubmed PY - 2010/9/10/medline SP - 12017 EP - 27 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 16 IS - 39 N2 - Monophosphine-o-carborane has four competitive coordination modes when it coordinates to metal centers. To explore the structural transitions driven by these competitive coordination modes, a series of monophosphine-o-carborane Ir,Rh complexes were synthesized and characterized. [Cp*M(Cl)(2){1-(PPh(2))-1,2-C(2)B(10)H(11)}] (M=Ir (1a), Rh (1b); Cp*=η(5)-C(5)Me(5)), [Cp*Ir(H){7-(PPh(2))-7,8-C(2)B(9)H(11)}] (2a), and [1-(PPh(2))-3-(η(5)-Cp*)-3,1,2-MC(2)B(9)H(10)] (M=Ir (3a), Rh (3b)) can be all prepared directly by the reaction of 1-(PPh(2))-1,2-C(2)B(10)H(11) with dimeric complexes [(Cp*MCl(2))(2)] (M=Ir, Rh) under different conditions. Compound 3b was treated with AgOTf (OTf=CF(3)SO(3) (-)) to afford the tetranuclear metallacarborane [Ag(2)(thf)(2)(OTf)(2){1-(PPh(2))-3-(η(5)-Cp*)-3,1,2-RhC(2)B(9)H(10)}(2)] (4b). The arylphosphine group in 3a and 3b was functionalized by elemental sulfur (1 equiv) in the presence of Et(3)N to afford [1-{(S)PPh(2)}-3-(η(5)-Cp*)-3,1,2-MC(2)B(9)H(10)] (M=Ir (5a), Rh (5b)). Additionally, the 1-(PPh(2))-1,2-C(2)B(10)H(11) ligand was functionalized by elemental sulfur (2 equiv) and then treated with [(Cp*IrCl(2))(2)], thus resulting in two 16-electron complexes [Cp*Ir(7-{(S)PPh(2)}-8-S-7,8-C(2)B(9)H(9))] (6a) and [Cp*Ir(7-{(S)PPh(2)}-8-S-9-OCH(3)-7,8-C(2)B(9)H(9))] (7a). Compound 6a further reacted with nBuPPh(2), thereby leading to 18-electron complex [Cp*Ir(nBuPPh(2))(7-{(S)PPh(2)}-8-S-7,8-C(2)B(9)H(10))] (8a). The influences of other factors on structural transitions or the formation of targeted compounds, including reaction temperature and solvent, were also explored. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/20827699/The_versatile_coordination_modes_of_monophosphine_o_carborane_in_the_formation_of_iridium_and_rhodium_complexes:_synthesis_reactivity_and_characterization_ L2 - https://doi.org/10.1002/chem.201001278 DB - PRIME DP - Unbound Medicine ER -

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The versatile coordination modes of monophosphine-o-carborane in the formation of iridium and rhodium complexes: synthesis, reactivity, and characterization.Chemistry. 2010 Oct 18; 16(39):12017-27.C