Three-coordinate RhX[P(C6H11)3]2, their reactions with N2 and O2, and the trans-influence in RhX[P(C6H11)3]2L (X = anionic, L = neutral ligand)

Gaal, H.L.M. van; BEKEROM, F. L. A. VAN DEN

doi:10.1016/s0022-328x(00)81423-0

Cited by 103 publications

(42 citation statements)

References 30 publications

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“…Some of these previously reported structures are analogous to the one which we report here, having the general formula trans-[L 2 Rh(N 2 )X] (X = halogen or hydrogen), where in our case L is the NHC IPr. When L = PiPr 3 [28,29] or PCy 3 [30,31] and X = Cl, the reported structures have nearly identical ν(N-N) stretches to those found in this investigation (2100 and 2103 cm -1 , respectively). In the case of the PiPr 3 complex, the Rh-N and N-N bond lengths [1.885(4) and 0.958 (5)] are similarly reasonably close to those observed by us for compound 2.…”

Section: Introductionsupporting

confidence: 76%

Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N‐Heterocyclic Carbene Ligands

2009

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The rhodium bis-carbene complex [Rh(IPr) 2 (N 2 )Cl], where IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, has been synthesized and characterized. The complex is a rare example of a four-coordinate rhodium complex featuring nitrogen bound end-on. While quite stable as a solid under inert atmosphere, in solution the N 2 ligand has been found to be quite labile. This lability has been exploited in the synthe-

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Section: Introductionsupporting

confidence: 76%

Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N‐Heterocyclic Carbene Ligands

2009

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“…After removal of the solvent and chromatographic workup or extraction of the residue with pentane blue-violet or green mycrocrystalline solids with the analytical composition corresponding to 9 and 10 (Scheme 3) were isolated in 69 ± 75 % yield. Typical spectroscopic data of 9 and 10 are the signal for the RhCCH proton at d 1.66 ppm (9) observations, [12] we interpret the initial change of color from red to yellow as indicative for the formation of an (h 2 -alkyne)rhodium(i) or an alkynyl(hydrido)rhodium(iii) intermediate.…”

mentioning

confidence: 79%

“…2 Rh) 207.5 Hz. [9] Therefore, it seems that 4 b is a 14-electron monomer that can not only be stabilized by dimerization but also by intramolecular C ± H activation, the latter being a reversible process. We note that both by dimerization and intramolecular C ± H activation the molecule approaches a situation in which each rhodium center formally possesses a 16-electron count.…”

mentioning

confidence: 99%

“…The mixture of 4a ± c reacts with CO, ethene, and phenylacetylene to give the square-planar compounds trans-[RhCl(L)(L 1 ) 2 ] (L CO (5), C 2 H 4 (6), CCHPh (9) (1) is probably one of the most reactive rhodium(i) compounds known to date. [1] It reacts not only with H 2 , O 2 , N 2 , CO, and C 2 H 4 but also with terminal alkynes to give stepwise p-alkyne-, alkynyl(hydrido)-, and vinylidenerhodium derivatives.…”

mentioning

confidence: 99%

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Rhodium(I) and Rhodium(III) Complexes Formed by Coordination and CH Activation of Bulky Functionalized Phosphanes

Canepa

Brandt

Ilg

et al. 2003

Chemistry A European J

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The reaction of [[RhCl(C(8)H(14))(2)](2)] (2) with iPr(2)PCH(2)CH(2)C(6)H(5) (L(1)) led, via the isolated dimer [[RhCl(C(8)H(14))(L(1))](2)] (3), to a mixture of three products 4 a-c, of which the dinuclear complex [[RhCl(L(1))(2)](2)] (4 a) was characterized by Xray crystallography. The mixture of 4a-c reacts with CO, ethene, and phenylacetylene to give the square-planar compounds trans-[RhCl(L)(L(1))(2)] (L=CO (5), C(2)H(4) (6), C=CHPh (9)). The corresponding allenylidene(chloro) complex trans-[RhCl(=C=C=CPh(2))(L(1))(2)] (11), obtained from 4 a-c and HC triple bond CC(OH)Ph(2) via trans-[RhCl[=C=CHC(OH)Ph(2)](L(1))(2)] (10), could be converted stepwise to the related hydroxo, cationic aqua, and cationic acetone derivatives 12-14, respectively. Treatment of 2 and [[RhCl(C(2)H(4))(2)](2)] (7) with two equivalents of tBu(2)PCH(2)CH(2)C(6)H(5) (L(2)) gave the dimers [[RhCl(C(8)H(14))(L(2))](2)] (15) and [[RhCl(C(2)H(4))(L(2))](2)] (16), which both react with L(2) in the molar ratio of 1:2 to afford the five-coordinate aryl(hydrido)rhodium(III) complex [RhHCl(C(6)H(4)CH(2)CH(2)PtBu(2)-kappa(2)C,P)(L(2))] (17) by C-H activation. The course of the reactions of 17 with CO, H(2), PhC triple bond CH, HCl, and AgPF(6), leading to the compounds 19-21, 24, and 25 a, respectively, indicate that the coordinatively unsaturated isomer of 17 with the supposed composition [RhCl(L(2))(2)] is the reactive species. Labeling experiments using D(2), DCl, and PhC triple bond CD support this proposal. With either [Rh(C(8)H(14))(eta(6)-L(2)-kappaP]PF(6) or [Rh(C(2)H(4))(eta(6)-L(n)-kappaP]PF(6) (n=1 and 2) as the starting materials, the corresponding halfsandwich-type complexes 27, 28, and 32 were obtained. The nonchelating counterpart of the dihydrido compound 32 with the composition [RhH(2)(PiPr(3))(eta(6)-C(6)H(6))]PF(6) (35) was prepared stepwise from [Rh(C(2)H(4))(PiPr(3))(eta(6)-C(6)H(6))]PF(6) and H(2) in acetone via the tris(solvato) species [RhH(2)(PiPr(3))(acetone)(3)]PF(6) (34) as intermediate. The synthesis of the bis(chelate) complex [Rh(eta(4)-C(8)H(12))(C(6)H(5)OCH(2)CH(2)PtBu(2)-kappa(2)O,P)]BF(4) (39) is also described. Besides 4 a, the compounds 17, 25 a, and 39 have been characterized by Xray crystal structure analysis.

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“…20 The only NMR characterisation of a tri-coordinate complex of this type was the proposed synthesis and characterisation of [Rh(PCy 3 ) 2 Cl] tri-coordinated complexes. 21 Comparison with the 31 P NMR spectrum of the corresponding dimer [Rh 2 (PCy 3 ) 4 (µ 2 -Cl) 2 ] revealed a slight change in the value of J P-Rh . However the monomerisation of the [Rh 2 (PCy 3 ) 4 (µ 2 -Cl) 2 ] complex was not observed or proved.…”

Section: Resultsmentioning

confidence: 99%

Monomerisation of [Rh₂(1,3-Bis-(Diphenylphosphino)-Propane)₂(μ₂-Cl)₂] Detected by Pulsed Gradient Spin Echo Spectroscopy and ³¹P Nmr Monitoring of Metathesis Experiments

Mannu

Ferro

Möller

et al. 2018

Journal of Chemical Research

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A pulsed gradient spin echo experiment on [Rh2(1,3-bis-(diphenylphosphino)-propane)2(μ2-Cl)2] complex has been conducted in order to shed light on the supposed monomerisation process of [Rh2(diphosphine)2(μ2-Cl)2] complexes in solution. Such a process should generate a 14-electron [Rh(diphosphine)Cl] complex, which has only been postulated to date. Metathesis experiments on [Rh2(1,3-bis-(diphenylphosphino)-propane)2(μ2-Cl)2] and [Rh2(bis[2-(diphenylphosphino)phenyl]ether)2(μ2-Cl)2] complexes, analysed by 31P NMR, reveal that monomerisation of [Rh2(diphosphine)2(μ2-Cl)2] complexes is not restricted to the case of 1,3-bis-(diphenylphosphino)propane.

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Three-coordinate RhX[P(C6H11)3]2, their reactions with N2 and O2, and the trans-influence in RhX[P(C6H11)3]2L (X = anionic, L = neutral ligand)

Cited by 103 publications

References 30 publications

Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N‐Heterocyclic Carbene Ligands

Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N‐Heterocyclic Carbene Ligands

Rhodium(I) and Rhodium(III) Complexes Formed by Coordination and CH Activation of Bulky Functionalized Phosphanes

Monomerisation of [Rh₂(1,3-Bis-(Diphenylphosphino)-Propane)₂(μ₂-Cl)₂] Detected by Pulsed Gradient Spin Echo Spectroscopy and ³¹P Nmr Monitoring of Metathesis Experiments

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Three-coordinate RhX[P(C6H11)3]2, their reactions with N2 and O2, and the trans-influence in RhX[P(C6H11)3]2L (X = anionic, L = neutral ligand)

Cited by 103 publications

References 30 publications

Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N‐Heterocyclic Carbene Ligands

Structure and Reactivity of Dinitrogen Rhodium Complexes Containing N‐Heterocyclic Carbene Ligands

Rhodium(I) and Rhodium(III) Complexes Formed by Coordination and CH Activation of Bulky Functionalized Phosphanes

Monomerisation of [Rh2(1,3-Bis-(Diphenylphosphino)-Propane)2(μ2-Cl)2] Detected by Pulsed Gradient Spin Echo Spectroscopy and 31P Nmr Monitoring of Metathesis Experiments

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Monomerisation of [Rh₂(1,3-Bis-(Diphenylphosphino)-Propane)₂(μ₂-Cl)₂] Detected by Pulsed Gradient Spin Echo Spectroscopy and ³¹P Nmr Monitoring of Metathesis Experiments