Trichlorostannato(diphosphine)rhodium(I) complexes. Crystal structure of [Rh(SnCl3)(1,5-cyclooctadiene)(dppp)]

García, Victoria; Garralda, María A.; Hernández, Ricardo; Monge, Ángeles; Pinilla, Elena

doi:10.1016/0022-328x(94)84138-1

Cited by 10 publications

(5 citation statements)

References 14 publications

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“…25 The Rh-Sn bond distances for 3, at 2.5644( 5) Å (Rh-Sn1), 2.5829(5) Å (Rh-Sn2), and 2.5662(5) Å (Rh-Sn3), are situated at the lower limit of known Rh-Sn bond lengths, which range from 2.526(1) Å in Rh[Sn(N t Bu) 2 SiMe 2 ] 5 Cl to 2.651(2) Å in [Rh(SnCl 3 )(NBD)(dppb)] (NBD ) norbornadiene, dppb ) 1,4bis(diphenylphosphino)butane). [26][27][28][29][30][31][32][33][34][35][36][37][38] A similar value is found The second complex, which is contained in the asymmetric unit, the solvent molecules, and H atoms have been omitted, and phenyl rings are symbolized by the ipso C for clarity. Selected bond distances and angles of this selected complex are summarized in Table 1.…”

Section: Resultsmentioning

confidence: 53%

“…The Rh−Sn bond distances for 3 , at 2.5644(5) Å (Rh−Sn1), 2.5829(5) Å (Rh−Sn2), and 2.5662(5) Å (Rh−Sn3), are situated at the lower limit of known Rh−Sn bond lengths, which range from 2.526(1) Å in Rh[Sn(N t Bu) 2 SiMe 2 ] 5 Cl to 2.651(2) Å in [Rh(SnCl 3 )(NBD)(dppb)] (NBD = norbornadiene, dppb = 1,4-bis(diphenylphosphino)butane). − A similar value is found in coordination compound [Rh(bipy‘)(Cp*)(SnB 11 H 11 )] (bipy‘ = 4,4‘-di- tert -butyl-2,2‘-bipyridine, Cp* = pentamethylcyclopentadiene), which includes also a tin-containing icosahedral boron cluster molecule, [SnB 11 H 11 ] 2- : Rh−Sn = 2.578(1) Å. Complex 3 adopts nearly perfect trigonal bipyramidal symmetry with negligible distortion, which is reflected in the axial bond angle of P1−Rh−P2, which is close to linearity at 175.90(5)°, the in-plane bond angles Sn−Rh−Sn, with an average value of 119.99°, and the P−Rh−Sn angles between the perpendicular axis and the plane, with an average value of 90.03°.…”

Section: Resultsmentioning

confidence: 98%

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1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

Joosten¹,

Weissinger²,

Kirchmann³

et al. 2007

Organometallics

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The synthesis of [MePPh 3 ][SnCB 10 H 11 ] is presented together with its structural, NMR, and 119 Sn Mo ¨ssbauer spectroscopical characterization. Two transition metal complexes, [Au 4 (PPh 3 ) 4 (SnCB 10 H 11 ) 2 ] and [Bu 4 N] 2 [Rh(PPh 3 ) 2 (SnCB 10 H 11 ) 3 ], with the carbastannaborate coordinated at rhodium or gold via the tin atom are presented, and the structural and NMR spectroscopical data are discussed.

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Section: Resultsmentioning

confidence: 53%

Section: Resultsmentioning

confidence: 98%

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

Joosten¹,

Weissinger²,

Kirchmann³

et al. 2007

Organometallics

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“…The Rh–C distance is also longer than the Rh–C bond found in complex 1 , which can be explained by the stronger trans influence of the trichlorostannate in comparison to the chloride ligand . The Rh–Sn bond length of 2.55873(6) Å lies in the range of Rh–SnCl 3 derivatives reported earlier. − Coordination of the pyridine ligand at Rh(III) in complex 3 exhibits a typical Rh–N bond length of 2.221(5) Å, indicating trans coordination to a ligand with a strong trans influence. , The hydride ligand was placed in a calculated position and refined with a fixed geometry.…”

Section: Results and Discusssionmentioning

confidence: 69%

Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction

et al. 2015

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Starting from commercially available 4,4′-di-tert-butyldiphenylmethane the pincer ligand bis(4-tert-butyl-2-(diphenylphosphino)phenyl)methane (PCP) was prepared in two steps in moderate yield. Treatment of a solution of RhCl3·3H2O in a mixture of isopropyl alcohol and toluene with equimolar amounts of PCP gave the dimeric rhodium complex 1. In an electrophilic metalation a facially coordinated pincer complex is formed. When PCP is treated with [CODRhCl]2 in a solution of pyridine, the square-pyramidal complex 2 is generated where the bis-phosphine PCP acts as bidentate ligand that coordinates in a cis fashion. SnCl2 inserts into the Rh–Cl bond of 2, which results in an oxidative addition of one of the methylene C–H bonds to form the Rh(III) complex 3, where the PCP ligand coordinates in a meridional way. A 2 equiv portion of PCP reacts with 1 equiv of [CODRhCl]2 in the presence of the electron-donating ligands HPhPC6H4NMe2, PPh2Py, and PPh3, respectively, as well as with stanna- and germa-closo-dodecaborate to give the octahedral Rh(III) complexes 4–8. Attempts to remove the HCl with KOtBu from complexes 4–6 produces the planar Rh(I) compounds 9 and 10. No carbene formation has been observed.

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“…The ability of crystal-packing forces to influence the P−Rh−P bite angle over a span of 5 degrees indicates that ( S,S )- i -Pr-BPP is relatively flexible in its bond angle preference. Likewise, rhodium complexes of three other carbon-bridged bisphosphines have been reported to adopt bite angles from 86.0° in [Rh(SnCl 3 )(1,5-cyclooctadiene)(Ph 2 PCH 2 CH 2 CH 2 PPh 2 )] to 96.97° in Rh(η 3 -CH 2 Ph)[( i- Pr) 2 PCH 2 CH 2 CH 2 P( i -Pr) 2 ] . The hydroformylation results obtained with ( S,S )-Ph-BPP suggest that bite angles near that found for ( S,S )-Ph-BPE can be accessed during the catalytic cycle.…”

Section: Resultsmentioning

confidence: 99%

“…of 5 degrees indicates that (S,S)-i-Pr-BPP is relatively flexible in its bond angle preference. Likewise, rhodium complexes of three other carbon-bridged bisphosphines have been reported to adopt bite angles from 86.0°in [Rh(SnCl 3 )(1,5-cyclooctadiene)(Ph 2 PCH 2 CH 2 CH 2 PPh 2 )]20 to 96.97°in Rh(η 3 -CH 2 Ph)[(i-Pr) 2 PCH 2 CH 2 CH 2 P(i-Pr) 2 ].…”

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confidence: 99%

Bridging Group Effects in Chelating Bis(2,5-diphenylphospholane) Ligands for Rhodium-Catalyzed Asymmetric Hydroformylation

Axtell¹,

Klosin²,

Whiteker³

et al. 2009

Organometallics

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A series of seven bis(2,5-diphenylphospholane) ligands has been evaluated for utility in rhodiumcatalyzed asymmetric hydroformylation. The ligands differ in the nature of the moiety that bridges the two phospholane rings. Hydroformylation of styrene, vinyl acetate, and allyl cyanide was performed in tandem using parallel pressure vessels. Significant differences in rate, regioselectivity, and enantioselectivity were observed between catalysts. Ligands with two-carbon bridges exhibited selectivities comparable to the ethylene-bridged (S,S)-Ph-BPE. Electron-deficient heterocyclic bridges (pyrazine and quinoxaline) gave increased rates over (S,S)-Ph-BPE. Bis(2,5-diphenylphospholane) ligands with -CH 2 -, -CH 2 CH 2 CH 2 -, and 1,1′-ferrocenyl bridges led to significantly lower selectivities and rates than (S,S)-Ph-BPE. X-ray crystal structures of [(S,S)-Ph-Quinoxaline]Rh(acac), [(R,R)-Ph-BPM]Rh(acac), and [(S,S)-Ph-5-Fc]Rh(acac) are reported. The P-Rh-P bite angles in these complexes are 87.46(3)°, 74.10(5)°, and 99.06(3)°, respectively. As with asymmetric olefin hydrogenation using bis-phospholane ligands, the maximum enantioselectivity in asymmetric hydroformylation was found with bis-phospholanes that adopt P-Rh-P bite angles near 85°.

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Trichlorostannato(diphosphine)rhodium(I) complexes. Crystal structure of [Rh(SnCl3)(1,5-cyclooctadiene)(dppp)]

Cited by 10 publications

References 14 publications

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction

Bridging Group Effects in Chelating Bis(2,5-diphenylphospholane) Ligands for Rhodium-Catalyzed Asymmetric Hydroformylation

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Trichlorostannato(diphosphine)rhodium(I) complexes. Crystal structure of [Rh(SnCl3)(1,5-cyclooctadiene)(dppp)]

Cited by 10 publications

References 14 publications

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

1,2-Carbastanna-closo-dodecaborate, a New Tin Ligand in Coordination Chemistry: Synthesis, Structure, and Reactivity

Different Coordination Modes of the Ph2PCsp3PPh2 Pincer Ligand in Rhodium Complexes as a Consequence of Csp3–H Metal Interaction

Bridging Group Effects in Chelating Bis(2,5-diphenylphospholane) Ligands for Rhodium-Catalyzed Asymmetric Hydroformylation

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Different Coordination Modes of the Ph₂PC_sp³PPh₂ Pincer Ligand in Rhodium Complexes as a Consequence of C_sp³–H Metal Interaction