Interaction of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}rhodium(I) with hydrocarbons. X-ray molecular structure of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}chlorohydridorhodium(III)

Nemeh, S.; Jensen, Craig M.; Binamira-Soriaga, E.; Kaska, William C.

doi:10.1021/om50004a034

Cited by 115 publications

(97 citation statements)

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“…The two RhÀP bond lengths are slightly longer than in the related, more symmetrical chelate complex [RhHCl-(tBu 2 PCH 2 C 6 H 3 CH 2 PtBu 2 -k 3 P,C,P)] (18) obtained from RhCl 3 ¥ 3 H 2 O and 1.5-C 6 H 4 (CH 2 PtBu 2 ) 2 in 2-propanol/water under reflux. [16] In contrast, the RhÀC31 bond length of 17 (1.967(5) ä) is slightly shorter than in 18 (1.999(7) ä) and in the related hydrido and methyl complexes [RhHCl{CH(CH 2 CH 2 PtBu 2 ) 2 -k 3 P,C,P}] (2.082(2) ä) [17] and [RhCH 3 Cl{tBu 2 PCH 2 C 6 H-3.5-(CH 3 ) 2 CH 2 PtBu 2 -k 3 P,C,P}] (2.02(2) ä), [18] respectively. The P1-Rh-P2 axis of 17 is significantly bent (160.18 (5)8), which could be due both to steric hindrance between the phosphane substituents and the strain of the chelate ring.…”

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confidence: 99%

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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mentioning

confidence: 99%

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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“…Thus, most of the information collected for this system, including catalytic and electrochemical experiments, led the authors to conclude that the PCP pincer system (16) is just the second best of the series tested in this study and that the ratedetermining step for the electrochemical reduction of CO 2 using this compound is probably the formation of an intermediate (19) such as that shown in Scheme 2.12. However, most of the efforts to prepare this species (19) independently were unsuccessful.…”

Section: Palladium and Platinummentioning

confidence: 79%

“…This compound contains a tridentate pincer ligand in which all three donors are carbenes (Scheme 2. 19). The structure of complex (37) was fully determined by single-crystal X-ray diffraction analysis.…”

Section: Palladium and Platinummentioning

confidence: 99%

“…However, Kaska and coworkers, in 1983 [19], retook the work carried by Shaw and coworkers and carried out similar reactions (Scheme 2.21) of the (PCP)Rh(III) pincer complex (38) with carbon monoxide in the presence of the very basic compound NaN (Si(CH 3 ) 3 ) 2 obtaining the same species (40). Later, in the study of the reactivity of the (PCP)Rh(I) complex (38), Kaska and coworkers [20] realized that the reaction of this compound with CO 2 was, in fact, a CO 2 reducing process to water and CO in what amounted to be a reversal of the water gas shift reaction.…”

Section: Rhodiummentioning

confidence: 99%

“…Although the authors claimed the observation of this sort of species, the evidence shown was not conclusive [19]. However, in 2002 Kaska and Mayer retook the issue by making variations on the PCP ligand to provide, this time, hard evidence including single-crystal X-ray diffraction studies for the characterization of these PCP pincer double cyclometallated species.…”

Section: Iridiummentioning

confidence: 99%

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Die Wagenradkomplexe A sind neuartige, nanogroße Hexametallspezies, die ausgehend von den persubstituierten Benzolen C6[3,5‐(CH2Y)2C6H3] zugänglich sind (Y=NMe2, P(O)Ph2, PPh2, SPh). Die Molekülstruktur von A (Y=SPh, MLn=PdCl) ist C3‐symmetrisch mit Pd‐Pd‐Abständen zwischen radial benachbarten Zentren von 7.339(2) und 8.006(2) Å und einem Pd‐Pd‐Abstand zwischen diametral gegenüberliegenden Zentren von 15.340(2) Å. Wegen ihrer Größe sind Hexametallspezies wie A potentielle homogene Katalysatoren, die durch Nanomembran‐Filtrationsverfahren leicht abgetrennt und so zurückgewonnen werden können.

show abstract

Interaction of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}rhodium(I) with hydrocarbons. X-ray molecular structure of {2,6-bis[(di-tert-butylphosphino)methyl]phenyl}chlorohydridorhodium(III)

Cited by 115 publications

References 2 publications

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

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

Reactivity of Pincer Complexes Toward Carbon Monoxide

Design neuartiger Hexametall-Wagenradmoleküle aus persubstituierten Benzolverbindungen

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