.kappa.2-.kappa.3 Isomerism in Rhodium(I) Tris(pyrazolyl)borate Complexes of the Type Tp3R,4R,5RRh(LL) (LL = 2CO, COD, and NBD) and Their Dynamic Behavior in Solution. X-ray Crystal Structure of TpMeRh(NBD)

Bucher, Urs E.; Currao, Antonio; Nesper, Reinhard; Rueegger, H.; Venanzi, L. M.; Younger, Elizabeth

doi:10.1021/ic00105a015

Cited by 142 publications

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“…These features have also been observed for the TBP complexes [Rh(NBD)Tp Me )] 20 and [Rh-(NBD)(bis(indazol-1-yl)pyridin-2′-ylmethane))]PF 6 21 ( Table 13). …”

Section: Synthesis and Characterization Of [Rhcl(26-(c(h)dn-rsupporting

confidence: 56%

Reactions of [RhCl(diene)]₂with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

et al. 1997

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Reactions of [RhCl(diene)]2 (diene=NBD,COD) with bi-and terdentate nitrogen ligands. X-ray structures of five-coordinate complexes Haarman, H.F.; Bregman, F.R.; Ernsting, J.M.; Veldman, N.; Spek, A.L.; Vrieze, K. Published in: Organometallics DOI:10.1021/om960760bLink to publication Citation for published version (APA):Haarman, H. F., Bregman, F. R., Ernsting, J. M., Veldman, N., Spek, A. L., & Vrieze, K. (1997). Reactions of [RhCl(diene)]2 (diene=NBD,COD) with bi-and terdentate nitrogen ligands. X-ray structures of five-coordinate complexes. Organometallics, 16, 54-67. DOI: 10.1021/om960760b General rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. Reaction of [RhCl(diene)] 2 (diene ) 1,5-cyclooctadiene (COD) or bicyclo[2.2.1] hepta-2,5-diene (NBD)) with the N-N-N nitrogen ligands 2,6-(C(R 1 )dN-R 2 ) 2 C 5 H 3 N in CD 2 Cl 2 or CH 2 Cl 2 yielded the five-coordinate complexes [RhCl(2,6-(C(H)dN-R 2 ) 2 C 5 H 3 N)(diene)] (diene ) NBD; R 2 ) i- Pr, t-Bu, and p-anisyl), which has been isolated for NBD but not for COD. A single-crystal X-ray determination showed that [RhCl(2,6-(C(H)dN-p-anisyl) 2 C 5 H 3 N)(NBD)] has a distorted trigonal bipyramidal configuration with the pyridyl N-atom, one imine N-atom, and one alkene double bond in the equatorial plane, while the second alkene bond and the chloride atom occupy the axial positions. This conformation containing one noncoordinated imine moiety is clearly retained at 183 K in CD 2 Cl 2 , as is also the case for the other complexes. For the COD complexes, the reaction is more complicated, as the intermediates that are observed depend on the substituents R 1 and R 2 of the N-N-N nitrogen ligand. The five-coordinate complexes [RhCl(2,6-(C(R 1 )dN-R 2 ) 2 C 5 H 3 N)(COD)] could be observed at low temperatures for R IntroductionRecently we reported novel Rh(I) complexes which were able to cleave C-Cl bonds of reagents such as dichloromethane, chloroform, benzyl chloride, and R,Rdichlorotoluene by oxidative addition. 1 By employment of N-N-N nitrogen ligands of the type 2,6-(C(R 1 )dN-R 2 ) 2 C 5 H 3 N (R 1 ) H, R 2 ) i-Pr, t-Bu, cyclohexyl, and p-anisyl; R 1 ) Me, R 2 ) p-anisyl and i-Pr), we succeeded in preparing very nucleophilic and very reactive Rh(I) complexes via reaction of [RhCl(alkene) 2 ] 2 (alkene ) cyclooctene or...

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“…These features have also been observed for the TBP complexes [Rh(NBD)Tp Me )] 20 and [Rh-(NBD)(bis(indazol-1-yl)pyridin-2′-ylmethane))]PF 6 21 ( Table 13). …”

Section: Synthesis and Characterization Of [Rhcl(26-(c(h)dn-rsupporting

confidence: 56%

Reactions of [RhCl(diene)]₂with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

et al. 1997

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“…The cationic five coordinate complexes [1] ± [7] are oxidised at lower potentials than that of [ [23] to [3]PF 6 converts [3] to square planar complex [18] 2 (Scheme 5 see below). Quite remarkably, this has virtually no effect on E [17] it seems reasonable to assume that stronger N 3Rh donation will result in stronger Rh 3C C back-donation. d( , [18] and of N Py relative to N Py-Me .…”

mentioning

confidence: 99%

Selective Oxidation of [RhI(cod)]+ by H2O2 and O2

et al. 1999

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“…Both in solution and in the solid state, 4 rearranges slowly during several months at room temperature to give 7 as the final product in the presence of traces of oxygen (Scheme 2). The structure of the 16 e complex 5 is supported by d 103 Rh = +1175.0, in the typical range known for similar 16 e complexes [5], in which the ªnormalº coordination mode (C) of a j 2 (N,N)-Tp* ligand is evident. As indicated by the d 31 P value (131.9), only one of the cycloheptatrienyl groups in 5 remains coordinated to the rhodium atom.…”

Section: Methodsmentioning

confidence: 60%

“…The tris(1-pyrazolyl)borate anion (Tp) and its ringsubstituted analogues (with various groups in the positions 3, 4, or 5), in particular tris(3,5-dimethyl-1-pyrazolyl)borate (Tp*), are versatile tridentate j 3 ((N,N,N) (A) and j ) and trihapto (j 3 ) rhodium diolefin complexes has been extensively studied [5]. Recently, another possible bidentate mode of coordination, i. e. 3 .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of [TpRh{P(C7H7)3}] - Competition between the Ligands Tris(3,5-dimethyl-1-pyrazolyl)borate (Tp) and Tris(1-cyclohepta-2,4,6-trienyl)phosphane. Proof of the κ2(N,B-H) Coordination Mode of the Tp* Ligand

Herberhold

Eibl

Milius

et al. 2000

Z. anorg. allg. Chem.

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.kappa.2-.kappa.3 Isomerism in Rhodium(I) Tris(pyrazolyl)borate Complexes of the Type Tp3R,4R,5RRh(LL) (LL = 2CO, COD, and NBD) and Their Dynamic Behavior in Solution. X-ray Crystal Structure of TpMeRh(NBD)

Cited by 142 publications

References 0 publications

Reactions of [RhCl(diene)]₂with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

Reactions of [RhCl(diene)]₂with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

Selective Oxidation of [RhI(cod)]+ by H2O2 and O2

Synthesis and Structure of [TpRh{P(C7H7)3}] - Competition between the Ligands Tris(3,5-dimethyl-1-pyrazolyl)borate (Tp) and Tris(1-cyclohepta-2,4,6-trienyl)phosphane. Proof of the κ2(N,B-H) Coordination Mode of the Tp* Ligand

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.kappa.2-.kappa.3 Isomerism in Rhodium(I) Tris(pyrazolyl)borate Complexes of the Type Tp3R,4R,5RRh(LL) (LL = 2CO, COD, and NBD) and Their Dynamic Behavior in Solution. X-ray Crystal Structure of TpMeRh(NBD)

Cited by 142 publications

References 0 publications

Reactions of [RhCl(diene)]2with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

Reactions of [RhCl(diene)]2with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

Selective Oxidation of [RhI(cod)]+ by H2O2 and O2

Synthesis and Structure of [Tp*Rh{P(C7H7)3}] - Competition between the Ligands Tris(3,5-dimethyl-1-pyrazolyl)borate (Tp*) and Tris(1-cyclohepta-2,4,6-trienyl)phosphane. Proof of the κ2(N,B-H) Coordination Mode of the Tp* Ligand

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Reactions of [RhCl(diene)]₂with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

Reactions of [RhCl(diene)]₂with Bi- and Terdentate Nitrogen Ligands. X-ray Structures of Five-Coordinate Complexes

Synthesis and Structure of [TpRh{P(C7H7)3}] - Competition between the Ligands Tris(3,5-dimethyl-1-pyrazolyl)borate (Tp) and Tris(1-cyclohepta-2,4,6-trienyl)phosphane. Proof of the κ2(N,B-H) Coordination Mode of the Tp* Ligand