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

Abstract

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...

Rational Design of Rhodium Complexes Featuring κ4‐N,N,N,N‐ and κ5‐N,N,N,P,P‐Bis(imino)pyridine Ligands

“…The metrical parameters determined for 1-Cl (Table 1) indicate that the geometry about the metal is distorted from idealized square planar with an N(1)-Rh(1)-N(3) angle of 159.19(11)°. It is important to note that the Rh( [32] and are remarkably undistinguished from the same distances reported for related trivalent (PDI)Rh(Cl) 2 (CH 2 Cl) complexes. Shortening of the C imine -C pyridine bonds relative to the distances expected for a neutral chelate [6] is also apparent with C(2)-C(3) and C(7)-C(8) distances of 1.452(5) Å and 1.467(4) Å, respectively.…”

“…Like the aforementioned basemetal examples, recent (PDI)Rh chemistry has been dominated by the use of bulky aryl imine substituents. [30][31][32] In one particularly relevant example, a monochloride complex bearing alkylamido imine substituents, ( MeCONHEt PDI)RhCl, was found to oxidatively add alkyl halides. [30][31][32] In one particularly relevant example, a monochloride complex bearing alkylamido imine substituents, ( MeCONHEt PDI)RhCl, was found to oxidatively add alkyl halides.…”

Isocyanide Insertion into the Palladium−Carbon Bond of Complexes Containing Bidentate Nitrogen Ligands: A Structural and Mechanistic Study

“…54 the exchange in complex 3b of the protons H4, H4′, H6, and H6′ with one another can be explained by a mechanism (see Scheme 1) in which during the site exchange of the two pyrimidine rings (i.e., exchange of H4 with H4′ and H6 with H6′), the two rings undergo an internal rotation around the C-C bond (i.e., exchange of H6 with H4 and H6′ with H4′). It is clear that the internal ligand rotation necessitates Pd-N bond breaking (see Scheme 1).…”

Square-planar rhodium(I) complexes with aromatic bent terdentate nitrogen ligands as candidates for rod-like extended materials †

“…13, 14 At low temperature (210 K) a series of resolved signals corresponding to a single species in slow exchange on the NMR timescale (>90% of the ligand speciation according to the integration of the signals) can be assigned by using { 1 H-1 H}-COSY spectra and NOE measurements (Fig. 5).…”