Side-on bonded dinitrogen and dioxygen complexes of rhodium(I). Synthesis and crystal structures of trans-chloro(dinitrogen)-, chloro-(dioxygen)-, and chloro(ethylene)-bis(tri-isopropylphosphine)rhodium(I)

Busetto, C.; D'alfonso, A.; Maspero, Frederico; Perego, G.; Zazzetta, Alessandro

doi:10.1039/dt9770001828

Cited by 122 publications

(64 citation statements)

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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: 75%

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: 75%

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

2009

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“…After the combined extracts were concentrated in vacuo to about 1 mL, a green solid precipitated. The precipitate was separated from the mother liquor, washed with pentane (5 Â 5 mL, 0 8C) and dried; yield 1 (11): The first part of the procedure is analogous to that described for 10. From 2 (518 mg, 0.72 mmol), L 1 (642 mg, 2.89 mmol) and HCCC(OH)Ph 2 (301 mg, 1.44 mmol) the precursor 10 was generated in situ.…”

Section: Methodsmentioning

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. [2] By a similar route, allenylidene as well as pentatetraenylidenerhodium(i) complexes have been obtained.…”

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confidence: 99%

“…Already after a few minutes (at room temperature), further signals appear and after 3 ± 4 h an equilibrium state is established. Besides 4 a, a second compound 4 c is present, the 1 H NMR spectrum of which shows in the high-field region a signal at d À 19.89 ppm being typical for a hydridorhodium species. The signal is split into a doublet of doublets of doublets due to one P couplings.…”

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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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“…Wir hatten in einer vorangegangenen Arbeit gezeigt, daß Rhodiumkomplexe des Typs trans- [RhCl(RC=CH) tonen der Triisopropylphosphan-Liganden stets ein Dublett-von-virtuellen-Tripletts, was in Überein-stimmung mit früheren Beobachtungen [10,11] die /rarcs-Konfiguration bestätigt. Typisch an den 13 C-NMR-Spektren ist die Lage des Signals des C aAtoms des Vinyliden-Liganden, das im gleichen Bereich wie dasjenige eines metallgebundenen CarbenKohlenstoffatoms auftritt [12].…”

Section: Einführungunclassified

Synthese der ersten quadratisch-planaren Vinyliden-Komplexe des Vaska-Typs. Kristall- und Molekülstruktur von trans-[RhCl(=C=CHMe)(PPrⁱ ₃)₂] / Synthesis of the First Square-planar Vinylidene Complexes of the Vaska Type. Crystal and Molecular Structure of trans-[RhCl(=C=CHMe)(PPrⁱ ₃)₂]

Werner

Alonso

Otto

et al. 1988

Zeitschrift Für Naturforschung B

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Square-planar vinylidene rhodium complexes trans-[RhCl( = C=CHR)(PPri3)2] (X-XII) are prepared either by isomerization of trans-[RhCl(RC≡CH)(PPri3)2] in hexane at 50 °C or by elimination of pyridine from RhHCl(C≡CR)(py)(PPri3)2 in benzene at room temperature. The Xray structural analysis of XI (R = CH3) reveals that the CI-Rh=C=C fragment is almost linear, and that the planes formed by these atoms and C3 (carbon atom of the CH3 substituent) and by these atoms and P1 , P2 are perpendicular to each other. The Rh = C bond length is surprisingly short (177.5(6) pm) and supports the assumption that vinylidenes like CO are strong π-acceptor ligands.

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Side-on bonded dinitrogen and dioxygen complexes of rhodium(I). Synthesis and crystal structures of trans-chloro(dinitrogen)-, chloro-(dioxygen)-, and chloro(ethylene)-bis(tri-isopropylphosphine)rhodium(I)

Cited by 122 publications

References 0 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

Synthese der ersten quadratisch-planaren Vinyliden-Komplexe des Vaska-Typs. Kristall- und Molekülstruktur von trans-[RhCl(=C=CHMe)(PPrⁱ ₃)₂] / Synthesis of the First Square-planar Vinylidene Complexes of the Vaska Type. Crystal and Molecular Structure of trans-[RhCl(=C=CHMe)(PPrⁱ ₃)₂]

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Side-on bonded dinitrogen and dioxygen complexes of rhodium(I). Synthesis and crystal structures of trans-chloro(dinitrogen)-, chloro-(dioxygen)-, and chloro(ethylene)-bis(tri-isopropylphosphine)rhodium(I)

Cited by 122 publications

References 0 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

Synthese der ersten quadratisch-planaren Vinyliden-Komplexe des Vaska-Typs. Kristall- und Molekülstruktur von trans-[RhCl(=C=CHMe)(PPri 3)2] / Synthesis of the First Square-planar Vinylidene Complexes of the Vaska Type. Crystal and Molecular Structure of trans-[RhCl(=C=CHMe)(PPri 3)2]

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Synthese der ersten quadratisch-planaren Vinyliden-Komplexe des Vaska-Typs. Kristall- und Molekülstruktur von trans-[RhCl(=C=CHMe)(PPrⁱ ₃)₂] / Synthesis of the First Square-planar Vinylidene Complexes of the Vaska Type. Crystal and Molecular Structure of trans-[RhCl(=C=CHMe)(PPrⁱ ₃)₂]