Versatile reactivity of half-sandwich Ir and Rh complexes toward carboranylamidinates and their derivatives: synthesis, structure, and catalytic activity for norbornene polymerization.
Chemistry. 2011 Nov 18; 17(47):13298-307.C

Abstract

Synthesis, structure, and reactivity of carboranylamidinate-based half-sandwich iridium and rhodium complexes are reported for the first time. Treatment of dimeric metal complexes [{Cp*M(μ-Cl)Cl}(2)] (M = Ir, Rh; Cp* = η(5)-C(5)Me(5)) with a solution of one equivalent of nBuLi and a carboranylamidine produces 18-electron complexes [Cp*IrCl(Cab(N)-DIC)] (1 a; Cab(N)-DIC = [iPrN=C(closo-1,2-C(2)B(10)H(10))(NHiPr)]), [Cp*RhCl(Cab(N)-DIC)] (1 b), and [Cp*RhCl(Cab(N)-DCC)] (1 c; Cab(N)-DCC = [CyN=C(closo-1,2-C(2)B(10)H(10))(NHCy)]). A series of 16-electron half-sandwich Ir and Rh complexes [Cp*Ir(Cab(N')-DIC)] (2 a; Cab(N')-DIC = [iPrN=C(closo-1,2-C(2)B(10)H(10))(NiPr)]), [Cp*Ir(Cab(N')-DCC)] (2 b, Cab(N')-DCC = [CyN=C(closo-1,2-C(2)B(10)H(10)(NCy)]), and [Cp*Rh(Cab(N')-DIC)] (2 c) is also obtained when an excess of nBuLi is used. The unexpected products [Cp*M(Cab(N,S)-DIC)], [Cp*M(Cab(N,S)-DCC)] (M = Ir 3 a, 3 b; Rh 3 c, 3 d), formed through BH activation, are obtained by reaction of [{Cp*MCl(2)}(2)] with carboranylamidinate sulfides [RN=C(closo-1,2-C(2)B(10)H(10))(NHR)]S(-) (R = iPr, Cy), which can be prepared by inserting sulfur into the C-Li bond of lithium carboranylamidinates. Iridium complex 1 a shows catalytic activities of up to 2.69×10(6) g(PNB) mol(Ir)(-1) h(-1) for the polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst. Catalytic activities and the molecular weight of polynorbornene (PNB) were investigated under various reaction conditions. All complexes were fully characterized by elemental analysis and IR and NMR spectroscopy; the structures of 1 a-c, 2 a, b; and 3 a, b, d were further confirmed by single crystal X-ray diffraction.

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Authors+Show Affiliations

Yao ZJ

Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, Shanghai 200433, PR China.

Su G

No affiliation info available

Jin GX

No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

22009699

Citation

Yao, Zi-Jian, et al. "Versatile Reactivity of Half-sandwich Ir and Rh Complexes Toward Carboranylamidinates and Their Derivatives: Synthesis, Structure, and Catalytic Activity for Norbornene Polymerization." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 17, no. 47, 2011, pp. 13298-307.

Yao ZJ, Su G, Jin GX. Versatile reactivity of half-sandwich Ir and Rh complexes toward carboranylamidinates and their derivatives: synthesis, structure, and catalytic activity for norbornene polymerization. Chemistry. 2011;17(47):13298-307.

Yao, Z. J., Su, G., & Jin, G. X. (2011). Versatile reactivity of half-sandwich Ir and Rh complexes toward carboranylamidinates and their derivatives: synthesis, structure, and catalytic activity for norbornene polymerization. Chemistry (Weinheim an Der Bergstrasse, Germany), 17(47), 13298-307. https://doi.org/10.1002/chem.201101638

Yao ZJ, Su G, Jin GX. Versatile Reactivity of Half-sandwich Ir and Rh Complexes Toward Carboranylamidinates and Their Derivatives: Synthesis, Structure, and Catalytic Activity for Norbornene Polymerization. Chemistry. 2011 Nov 18;17(47):13298-307. PubMed PMID: 22009699.

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

TY - JOUR T1 - Versatile reactivity of half-sandwich Ir and Rh complexes toward carboranylamidinates and their derivatives: synthesis, structure, and catalytic activity for norbornene polymerization. AU - Yao,Zi-Jian, AU - Su,Ge, AU - Jin,Guo-Xin, Y1 - 2011/10/18/ PY - 2011/05/28/received PY - 2011/07/21/revised PY - 2011/10/20/entrez PY - 2011/10/20/pubmed PY - 2011/10/20/medline SP - 13298 EP - 307 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 17 IS - 47 N2 - Synthesis, structure, and reactivity of carboranylamidinate-based half-sandwich iridium and rhodium complexes are reported for the first time. Treatment of dimeric metal complexes [{Cp*M(μ-Cl)Cl}(2)] (M = Ir, Rh; Cp* = η(5)-C(5)Me(5)) with a solution of one equivalent of nBuLi and a carboranylamidine produces 18-electron complexes [Cp*IrCl(Cab(N)-DIC)] (1 a; Cab(N)-DIC = [iPrN=C(closo-1,2-C(2)B(10)H(10))(NHiPr)]), [Cp*RhCl(Cab(N)-DIC)] (1 b), and [Cp*RhCl(Cab(N)-DCC)] (1 c; Cab(N)-DCC = [CyN=C(closo-1,2-C(2)B(10)H(10))(NHCy)]). A series of 16-electron half-sandwich Ir and Rh complexes [Cp*Ir(Cab(N')-DIC)] (2 a; Cab(N')-DIC = [iPrN=C(closo-1,2-C(2)B(10)H(10))(NiPr)]), [Cp*Ir(Cab(N')-DCC)] (2 b, Cab(N')-DCC = [CyN=C(closo-1,2-C(2)B(10)H(10)(NCy)]), and [Cp*Rh(Cab(N')-DIC)] (2 c) is also obtained when an excess of nBuLi is used. The unexpected products [Cp*M(Cab(N,S)-DIC)], [Cp*M(Cab(N,S)-DCC)] (M = Ir 3 a, 3 b; Rh 3 c, 3 d), formed through BH activation, are obtained by reaction of [{Cp*MCl(2)}(2)] with carboranylamidinate sulfides [RN=C(closo-1,2-C(2)B(10)H(10))(NHR)]S(-) (R = iPr, Cy), which can be prepared by inserting sulfur into the C-Li bond of lithium carboranylamidinates. Iridium complex 1 a shows catalytic activities of up to 2.69×10(6) g(PNB) mol(Ir)(-1) h(-1) for the polymerization of norbornene in the presence of methylaluminoxane (MAO) as cocatalyst. Catalytic activities and the molecular weight of polynorbornene (PNB) were investigated under various reaction conditions. All complexes were fully characterized by elemental analysis and IR and NMR spectroscopy; the structures of 1 a-c, 2 a, b; and 3 a, b, d were further confirmed by single crystal X-ray diffraction. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/22009699/Versatile_reactivity_of_half_sandwich_Ir_and_Rh_complexes_toward_carboranylamidinates_and_their_derivatives:_synthesis_structure_and_catalytic_activity_for_norbornene_polymerization_ L2 - https://doi.org/10.1002/chem.201101638 DB - PRIME DP - Unbound Medicine ER -

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Versatile reactivity of half-sandwich Ir and Rh complexes toward carboranylamidinates and their derivatives: synthesis, structure, and catalytic activity for norbornene polymerization.Chemistry. 2011 Nov 18; 17(47):13298-307.C