Rhodium complexes with hydrotris(3-p-anisylpyrazol-1-yl)borate ligand TppAn. Intramolecular CH bond activation and dehydro-chlorination processes
TL;DR: In this article, the TppAn ligand in a bidentate η2-bonded form was observed in square planar complexes with the third uncoordinated pyrazolyl ring occupying an equatorial position or an axial position.
About: This article is published in Journal of Organometallic Chemistry.The article was published on 2000-06-30. It has received 12 citations till now. The article focuses on the topics: Hydride & Intramolecular force.
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TL;DR: Complexes 2-4 have been characterized by single-crystal X-ray diffraction analysis and a C-H bond activation byproduct [kappa(4)(N,N',N'',C(Ph))-Tp(Ph)Nd (4).
Abstract: Synthesis of new neodymium(III) phosphinidene complexes from a neodymium(III) phosphinidene iodide [(μ-PC6H3-2,6-iPr2)Nd(I)(THF)3]2 (1) was studied. The metathesis reaction of 1 with KC5Me5 (KCp*) gave a neodymium(III) pentamethylcyclopentadienyl phosphinidene complex [(μ-PC6H3-2,6-iPr2)(C5Me5)Nd(THF)]2 (2), and that with potassium hydrotris(pyrazolyl)borate KHB(3-phenylpz)3 (KTpPh) generated a neodymium(III) hydrotris(pyrazolyl)borate phosphinidene complex [(μ-PC6H3-2,6-iPr2)(TpPh*)Nd(THF)]2 (3) and a C–H bond activation byproduct [κ4(N,N′,N″,CPh)-TpPh]TpPhNd (4). Complexes 2–4 have been characterized by single-crystal X-ray diffraction analysis.
41 citations
TL;DR: In this article, the influence of pyrazol substituents on the properties of the Rh(I) complexes has been analyzed. And two crystalline polymorphs (yellow and red) have been isolated for [Rh(Cl)(CO) 2 (Hpz dp )] (12 ) in contrast to the single red crystalline form isolated for the related complexes [Rh (Cl)( CO) 2 ) (R=hp, op; 10 and 11 ).
31 citations
TL;DR: In this paper, the authors focus on those materials that conform to the generally accepted definition of "organometallic" and those that, while not strictly organometallic, are or have the potential to be of interest and utility to the chemist.
Abstract: Publisher Summary Poly (pyrazolyl)borate complexes of the group-10 triad are noticeably less numerous than many transition metals. However, the study of these materials has typically proven more systematic than for many others, dominated by investigation of reactivity traits with limited incidence of purely derivative examples. This chapter is concerned only with those materials that conform to the generally accepted definition of ‘‘organometallic,’’ and those that, while not strictly organometallic, are or have the potential to be of interest and utility to the organometallic chemist. Thus, the inclusion of all complexes featuring an M-C linkage– along with related metal hydrides, phosphanes, and nitrosyls– is implicit., Classical coordination compounds are included only where these possess substantiated or perceived utility to the field (e.g., synthetic precursors, catalysts) or serve to illustrate novel structural facets of far-reaching significance. Similar discretion is applied to the inclusion of more exotic materials that currently linger at the periphery of organometallic chemistry.
28 citations
TL;DR: In this paper, the energy of activation of the exchange between coordinated and uncoordinated pyrazolyls was estimated from variable-temperature 1H NMR measurements, and two ΔG⧧ values were found for heteroscorpionate TpPh,MeRh(COD) complexes.
21 citations
TL;DR: In this article, density functional calculations of the structure and relative energy of various isomers of the hydridotris(pyrazol-1-yl)borate ligand in Tp3R,5R rhodium(I) dicarbonyl complexes (R=H, Me) and their IR and 11B NMR spectra are compared to experimental observations.
20 citations
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TL;DR: The program is designed to be easy to use and general for all space groups and uses a conventional structure-factor calculation rather than a fast Fourier transform (FFT) summation, which is much slower than programs written specifically for macromolecules.
Abstract: Publisher Summary SHELXL-93 was originally written as a replacement for the refinement part of the small-molecule program SHELX-76. The program is designed to be easy to use and general for all space groups and uses a conventional structure-factor calculation rather than a fast Fourier transform (FFT) summation. The latter would be faster but in practice involves some small approximations and is not suitable for the treatment of anomalous dispersion or anisotropic thermal motion. The price to pay for the extra precision and generality is that SHELXL is much slower than programs written specifically for macromolecules. This is compensated for, to some extent, by the better convergence properties, reducing the amount of manual intervention required. A new version, SHELXL-97, was released in May 1997; this is the version described in the chapter. The changes are primarily designed to make the program easier to use for macromolecules. Advances in cryogenic techniques, area detectors, and the use of synchrotron radiation enable macromolecular data to be collected to higher resolution than was previously possible. In practice, this tends to complicate the refinement because it is possible to resolve finer details of the structure. It is often necessary to model alternative conformations, and in a few cases, even anisotropic refinement is justified.
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