Some complexes of rhodium(I), rhodium(II), and rhodium(III) containing tertiary t-butylphosphines as ligands

Masters, Christopher; Shaw, B. L.

doi:10.1039/j19710003679

Cited by 67 publications

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“…They all proceed under mild conditions (25 8C, 1 bar) and give the products in good (22,23) to excellent yields (19,20 (Figure 3) differ by the orientation of the phosphane sub- stituents along the P-Rh-P axis, thereby the most bulky tertbutyl groups probably playing the dominant role. The common feature of R .…”

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confidence: 98%

“…The dichloro(hydrido) compound 24 is formed as an orange air-stable solid that in the presence of triethylamine in C 6 D 6 regenerates the precursor quantitatively (Scheme 6). Regarding the structure of 24, we assume that in analogy to the structures of [RhHCl 2 (PiPr 3 ) 2 ] and [RhHCl 2 (PnPr 2 tBu) 2 ], determined crystallographically, [10,23] it corresponds to a square pyramid and not to a trigonal bipyramid. This proposal is indirectly supported by the observation that the resonances for the protons and carbon atoms of the C(CH 3 ) 3 groups are broadened in the 1 H and 13 C NMR spectra at 293 K, while they become sharp at 333 K. Moreover, if the 31 P NMR spectrum of 24 is measured at Rh coupling constant in each case being 96.6 Hz.…”

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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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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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“…Our first efforts of an attempted metathesis between ½RhClðBu t 2 PHÞ 3 [3] and sodium nitrite (excess) in chloroform, using a procedure similar as described for the synthesis of the complexes [RhX{P(OPh) 3 } 3 ] (e.g., X = SCN À or NO À 3 ) [7], afforded after workup a green compound in low yield. The microanalysis and the spectroscopic data (inclusive MS) were not consistent with a complex of the formula ½RhðNO 2 ÞðBu t 2 PHÞ 3 , however.…”

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confidence: 99%

“…Moreover, in recent years the chemistry of metal complexes containing secondary phosphines has been extensively studied by other authors, e.g., [2]. In the light of the synthesis of heteronuclear metal clusters using precursor complexes of the formula ½MClðBu t 2 PHÞ 3 ðM ¼ Rh; IrÞ [3,4] we were interested in the preparation of other mononuclear target compounds ½RhXðBu t 2 PHÞ 3 , e.g., with X ¼ NO À 2 . Therein we describe attempts to obtain the latter nitro species, which led in an unexpected manner to the complex trans-½RhðNOÞðNO 2 Þ 2 ðBu t 2 PHÞ 2 ð1Þ.…”

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Synthesis and X-ray crystal structure of the secondary phosphine complex

Böttcher¹,

Mereiter²

2004

Inorganic Chemistry Communications

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“…Paramagnetic rhodium(r1) complexes [RhC12L2] [L=Pcy3, P(O-tolyl),] are available[54] but the reaction of rhodium trichloride with less bulky phosphanes provides the more conventional RhC13L3…”

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The Versatility of Tertiary Phosphane Ligands in Coordination and Organometallic Chemistry

Mason

Meek

1978

Angew. Chem. Int. Ed. Engl.

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or animal feeds, is closely related to problems of world population and natural resources, together with changes in politics, social system, thought, and taste. It therefore seems difficult to predict future amino acid demands. Moreover, there are also economic restrictions; the lower the price the greater the demand, and the higher the price the smaller the demand. In spite of these problems, a favorable long term future can be predicted for the amino acid industry.Tertiary phosphanes form kinetically stable complexes with formal oxidation states of the metal ranging from + IV to -I ("electronic versatility"). Variously substituted phosphanes and polydentate, chelate forming phosphanes and polyphosphanes can be synthesized ("steric versatility"). Studies on complexes containing such ligands provide, inter alia, useful information about the metal-phosphorus bond, about the steric effects of the phosphane ligand, and about reactions of coordinated phosphanes.A large number of alkyl-and aryl-phosphanes are now available following the pioneering syntheses of tertiary phosphanes and arsanes by F. G. Mand'"] and J . Chatt['bl.of four currently important topics in the chemistry of transition metal complexes. Thus we present a reasonably objective survey of the minimum experimental observations needed to support our views on the nature of the metal-phosphorus

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Some complexes of rhodium(I), rhodium(II), and rhodium(III) containing tertiary t-butylphosphines as ligands

Cited by 67 publications

References 0 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

Synthesis and X-ray crystal structure of the secondary phosphine complex

The Versatility of Tertiary Phosphane Ligands in Coordination and Organometallic Chemistry

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