Heteronuclear and heterovalent diphenylphosphido-bridged complexes of rhodium, iridium and ruthenium. Crystal structure of [(C5Me5)ClRh(μ-Cl)(μ-PPh2)Rh(COD)] · Et2O (COD = 1,5-cyclooctadiene)

Esteban, M.; Pequerul, A.; Carmona, Daniel; Lahoz, Fernando J.; Martín, Alberto; Oro, Luis A.

doi:10.1016/0022-328x(91)86254-n

Cited by 22 publications

(11 citation statements)

References 22 publications

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“…The 31 P NMR spectra of 2a,b show large diagnostic 1 J PH coupling constants of ∼387 Hz and typical 1 J RhP values of ∼140 Hz. 7 Phosphinidene complexes are then obtained from 2a,b in a dehydrohalogenation-ligation sequence. For example, addition of a CH 2 Cl 2 solution of 2a to a solution of DBU and PPh 3 in toluene at room temperature affords dark green colored terminal rhodium complex 3 (Scheme 1) in high yield (89%).…”

Section: Resultsmentioning

confidence: 99%

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Terminal Phosphinidene Complexes Cp^R(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties

et al. 2003

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Novel terminal rhodium-and cobalt-complexed phosphinidenes, Cp*(PR 3 ) and Cp(PPh 3 )CodPAr (8), were obtained by dehydrohalogenation of the primary phosphine complexes Cp*RhCl 2 (PH 2 Ar) (2) and CpCoI 2 (PH 2 Ar) (7) in the presence of a phosphine. X-ray crystal structures are reported for Cp*(PPh 3 )RhdPMes* (3) and Cp(PPh 3 )CodPMes* (8). A comparative reactivity study and a computational survey were performed on the Co-, Rh-, and Ir-containing phosphinidene complexes. All react with organic dihalides to form phosphaalkenes, with the rhodium congener being far more reactive than the iridium and cobalt complexes. Density functional theory calculations give geometrical parameters and 31 P NMR chemical shifts in good agreement with experimental data. The rhodium congeners exhibit the most pronounced charge separation of the RhdP bond, which may explain its higher reactivity. The M-L bond is strong in all Cp(L)MdPH (M ) Co, Rh, Ir) complexes and inhibits reactivity at the metal center. Comparisons with the Zr-containing complex Cp 2 (PH 3 )Zr-PH are made.

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Section: Resultsmentioning

confidence: 99%

“…halogenation of the primary phosphine complexes Cp*RhCl 2 (PH 2 Ar) (2) and CpCoI 2 (PH 2 Mes*) (7) by DBU in the presence of a stabilizing phosphine ligand. X-ray crystal structures are presented for Cp*(PPh 3 )-RhdPMes* (3) and Cp(PPh 3 )CodPMes* (8), thereby completing the first (group 9) transition metal triad of phosphinidene complexes.…”

Section: Discussionmentioning

confidence: 99%

Terminal Phosphinidene Complexes Cp^R(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties

et al. 2003

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“…This complex, which appeared to be the catalyst resting state, is hypothesized to undergo two P-H oxidative addition events to form a Rh(V) bisphosphido dihydride complex, Cp*Rh(H) 2 (PPh 2 ) 2 (21). There is precedent in the literature for organometallic complexes that posses a formally Rh(V) center [89][90][91][92][93][94][95], and complexes of Cp*-supported rhodium complexes with a diphenylphosphido ligand are well known [96][97][98][99]. The Rh(V) intermediate would then reductively eliminate tetraphenyldiphosphine and hydrogen to then be trapped with two equivalents of Ph 2 PH to restore 20.…”

Section: B Late Metal Catalystsmentioning

confidence: 99%

Dehydrogenative Bond-Forming Catalysis Involving Phosphines

Waterman¹

2008

COC

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This review presents developments in the young field of dehydrogenative coupling reactions of phosphines. Catalytic phosphorus-element bond formation via dehydrocoupling has rapidly expanded since the first discoveries in the mid 1990s. A survey of the available catalysts, P-P and P-E products, and mechanistic understanding is presented with emphasis on the emerging synthetic applications of this reaction.

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“…An absorption in the area of 2440-2350 cm À 1 assignable to the PÀ H bond was not observed; however, there are other reports of secondary phosphane metal complexes, which also do not report the observation of such an absorption band. [47][48][49] In the 1 H NMR spectrum two signals for the diastereotopic ortho-tertbutyl groups are observed at δ = 1.33 and 1.36 ppm. In accord with the asymmetry of the compound four signals are observed for the cyclopentadienyl protons.…”

Section: Resultsmentioning

confidence: 99%

New Reactions of Cyclopentadienylnickel Chelates with Secondary Phosphane Tethers

2021

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In continuation of our research in cyclopentadienylalkylphosphane nickel chelates with secondary phosphane tethers the first cationic representatives of this class of compounds are reported. These were obtained by reaction of the respective bromo complex with tris(4-trifluoromethylphenyl)phosphane as well as with a number of alkyl and aryl isonitriles in the presence of indium tribromide. This Lewis acid is crucial for the success of the reactions leading to the respective tetrabromoindate salts. The compounds were characterized spectroscopically, including rare 14 N, 13 C couplings being observed. Finally, deprotonation experiments are reported, which provide some evidence for deprotonation taking place, although the expected phosphinidene chelates could not be isolated due to rapid decomposition.

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Heteronuclear and heterovalent diphenylphosphido-bridged complexes of rhodium, iridium and ruthenium. Crystal structure of [(C5Me5)ClRh(μ-Cl)(μ-PPh2)Rh(COD)] · Et2O (COD = 1,5-cyclooctadiene)

Cited by 22 publications

References 22 publications

Terminal Phosphinidene Complexes Cp^R(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties

Terminal Phosphinidene Complexes Cp^R(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties

Dehydrogenative Bond-Forming Catalysis Involving Phosphines

New Reactions of Cyclopentadienylnickel Chelates with Secondary Phosphane Tethers

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Heteronuclear and heterovalent diphenylphosphido-bridged complexes of rhodium, iridium and ruthenium. Crystal structure of [(C5Me5)ClRh(μ-Cl)(μ-PPh2)Rh(COD)] · Et2O (COD = 1,5-cyclooctadiene)

Cited by 22 publications

References 22 publications

Terminal Phosphinidene Complexes CpR(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties

Terminal Phosphinidene Complexes CpR(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties

Dehydrogenative Bond-Forming Catalysis Involving Phosphines

New Reactions of Cyclopentadienylnickel Chelates with Secondary Phosphane Tethers

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Terminal Phosphinidene Complexes Cp^R(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties

Terminal Phosphinidene Complexes Cp^R(L)MPAr of the Group 9 Transition Metals Cobalt, Rhodium, and Iridium. Synthesis, Structures, and Properties