Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity

Huo, Xian‐Kuan; Su, Ge; Jin, Guo‐Xin

doi:10.1039/b918272a

Cited by 23 publications

(16 citation statements)

References 55 publications

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“…[22] The reason is that the p-type interaction between the Ir center and the p orbital in the sulfur atom is destroyed in 18-electron Ir complexes. [23,24] The IR spectra of Norbornene polymerization: Iridium complex 1 a, which exhibits a C,N coordination mode, prompted us to investigate its application in homogeneous catalysis based on our previous work, [6c, 26] because the coordinatively labile imine group may dissociate from the metal center to produce a necessary vacancy for substrate complexion during the catalytic cycle. Carboranylamidinate iridium complex 1 a indeed shows higher catalytic activity in the polymerization of norbornene than our previous iridium complexes.…”

Section: Resultsmentioning

confidence: 99%

Versatile Reactivity of Half‐Sandwich Ir and Rh Complexes toward Carboranylamidinates and Their Derivatives: Synthesis, Structure, and Catalytic Activity for Norbornene Polymerization

Yao

Jin

2011

Chemistry A European J

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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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Section: Resultsmentioning

confidence: 99%

Versatile Reactivity of Half‐Sandwich Ir and Rh Complexes toward Carboranylamidinates and Their Derivatives: Synthesis, Structure, and Catalytic Activity for Norbornene Polymerization

Yao

Jin

2011

Chemistry A European J

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“…The molecular structure reveals that the geometry at the iridium(III) center is a three‐legged piano‐stool motif with iridium atom coordinated by the η 5 ‐Cp*, one P atom of 1‐PPh 2 ‐1,2‐C 2 B 10 H 11 , and two chloride atoms; consequently, it can be described as pseudo‐octahedron in which η 5 ‐Cp* group occupies three fac coordination sides. The IrP and IrCl bond lengths are comparable to those of analogous complexes 7…”

Section: Resultsmentioning

confidence: 64%

The Versatile Coordination Modes of Monophosphine‐o‐Carborane in the Formation of Iridium and Rhodium Complexes: Synthesis, Reactivity, and Characterization

Huo

Jin

2010

Chemistry A European J

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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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“…Since the central methine carbon atom is not coordinated to Rh, these are zwitterionic complexes as it is found in numerous structurally similar dppm eH -k 2 P,P 0 complexes [36,38,39]. Till now, in literature zwitterionic complexes with P^S ligands are described only in which the anionic carbon atom is part of a carboborane [40] or of a ring system [41]. The assignment of the coordination mode of the flexidentate anionic [Ph 2 PCHS(O)Ph] ligand in 20b (kP,kO) and 21b (kP,kS) was performed on the same basis as it was done for the appropriate cationic rhodium complexes 13b and 14b (see Section 2.2.2.…”

Section: Organorhodium Intramolecular Coordination and Zwitterionic Cmentioning

confidence: 97%

Rhodium(I) complexes with κP coordinated ω-phosphinofunctionalized alkyl phenyl sulfide, sulfoxide and sulfone ligands and their reactions with sodium bis(trimethylsilyl)amide and Ag[BF4]

Block

Bette

Wagner

et al. 2011

Journal of Organometallic Chemistry

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Neutral and zwitterionic half-sandwich Ir, Rh complexes supported by P,S-substituted o-carboranyl ligands: Synthesis, characterization and reactivity

Cited by 23 publications

References 55 publications

Versatile Reactivity of Half‐Sandwich Ir and Rh Complexes toward Carboranylamidinates and Their Derivatives: Synthesis, Structure, and Catalytic Activity for Norbornene Polymerization

Versatile Reactivity of Half‐Sandwich Ir and Rh Complexes toward Carboranylamidinates and Their Derivatives: Synthesis, Structure, and Catalytic Activity for Norbornene Polymerization

The Versatile Coordination Modes of Monophosphine‐o‐Carborane in the Formation of Iridium and Rhodium Complexes: Synthesis, Reactivity, and Characterization

Rhodium(I) complexes with κP coordinated ω-phosphinofunctionalized alkyl phenyl sulfide, sulfoxide and sulfone ligands and their reactions with sodium bis(trimethylsilyl)amide and Ag[BF4]

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