2006
DOI: 10.1039/b608293a
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Abstract: The Ir(III) compound Tp(Ms'')Ir(N2), that contains a pentadentate, doubly metalated 3-mesityl substituted tris(pyrazolyl)borate ligand, induces the cleavage of C-H and C-Cl bonds of CH2Cl2 to yield a highly electrophilic chlorocarbene Ir=C(H)Cl complex.

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Cited by 19 publications
(13 citation statements)
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“…In parallel studies,9 we also demonstrated that an Ir III complex of a doubly metallated Tp Mes ligand (Tp Mes =hydrotris(3 ‐ mesitylpyrazolyl)borate) cleaved dichloromethane cleanly to produce a monochloro carbene ligand, :C(H)Cl, with the remaining Cl and H atoms adding to the metal and to one of the IrCH 2 bonds of the starting compound, respectively (Scheme ).…”
Section: Methodsmentioning
confidence: 85%
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“…In parallel studies,9 we also demonstrated that an Ir III complex of a doubly metallated Tp Mes ligand (Tp Mes =hydrotris(3 ‐ mesitylpyrazolyl)borate) cleaved dichloromethane cleanly to produce a monochloro carbene ligand, :C(H)Cl, with the remaining Cl and H atoms adding to the metal and to one of the IrCH 2 bonds of the starting compound, respectively (Scheme ).…”
Section: Methodsmentioning
confidence: 85%
“… Previous reactivity studies on Tp′Ir III systems (a),6 and (b)9 relevant to the iridabenzene synthesis reported herein (c). exc.=saturated.…”
Section: Methodsmentioning
confidence: 91%
“…Interestingly, C 2 H 4 did not afford a related methyl-substituted iridabenzene but inserted instead into an Ir À C bond giving a H 2 O-stabilized iridacycloheptadiene. [8] In parallel studies, [9] we also demonstrated that an Ir III complex of a doubly metallated Tp Mes ligand (Tp Mes = hydrotris(3-mesitylpyrazolyl)borate) cleaved dichloromethane cleanly to produce a monochloro carbene ligand, :C(H)Cl, with the remaining Cl and H atoms adding to the metal and to one of the Ir À CH 2 bonds of the starting compound, respectively (Scheme 1 b).…”
mentioning
confidence: 83%
“…Interestingly, C 2 H 4 did not afford a related methyl-substituted iridabenzene but inserted instead into an Ir À C bond giving a H 2 O-stabilized iridacycloheptadiene. [8] In parallel studies, [9] we also demonstrated that an Ir III complex of a doubly metallated Tp Mes ligand (Tp Mes = hydrotris(3-mesitylpyrazolyl)borate) cleaved dichloromethane cleanly to produce a monochloro carbene ligand, :C(H)Cl, with the remaining Cl and H atoms adding to the metal and to one of the Ir À CH 2 bonds of the starting compound, respectively (Scheme 1 b).Encompassing these two reactivity modes, we now report the formation of the first parent metallabenzene (complex 2 in Scheme 1 c) in the reaction of the compound [TpIr(C 2 H 4 ) 2 ] (1) [10] (Tp = hydrotris(pyrazolyl)borate) with acetylene in CH 2 Cl 2 .A solution of complex 1 (50 mg, 0.1 mmol) in CH 2 Cl 2 (20 mL) saturated with acetylene [11] (glass ampoule, À60 8C, 1 atm) was allowed to reacted from À60 8C to room temper-ature to yield quantitatively (by NMR spectroscopy) an approximately 1:1 mixture of the iridabenzene 2 and the bchlorinated vinyl hydride complex 3 (Scheme 2). Under the above conditions, the reaction outcome is highly reproducible but the yield of the iridabenzene is highly sensitive to deviations from them, for example, if C 2 H 2 saturation is carried out at À20 8C the ratio of complexes 2 and 3 becomes ca.…”
mentioning
confidence: 99%
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