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Transition-metal complexes with bidentate ligands spanning trans-positions. V. Crystal and molecular structures of complexes [RhCl(CO) (1)] and [PdCl2(1)]; 1 = 2,11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene

✍ Scribed by Fiorella Bachechi; Luigi Zambonelli; Luigi M. Venanzi

Publisher
John Wiley and Sons
Year
1977
Tongue
German
Weight
483 KB
Volume
60
Category
Article
ISSN
0018-019X

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✦ Synopsis

The structures of [RhCl(CO)(l)] and [PdC1,(1)], where 1 is the bidentate ligand (C6H5)2P . CH2 . ClsHlo . CH2 . P (C6H5),, have been determined from threedimensional X-ray counter data collected on single crystals of the C6H5. CN solvates. The two compounds are isomorphous and crystallize in the triclinic system, space group P 1, Z = 2 : a= 14.580(8), b= 13.029(10), c= 11.909(6) A, a = 106.33 (5), p = 100.47 (4), y = 95.73 (5)" for the rhodium complex; a= 14.361 ( 5 ) , b= 13.044(7), c= 11.897(4) A, a = 105.97(4), p= 100.27(3), y=94.76(4)", for the palladium complex. In both complexes the metal atom is four-coordinate with slightly distorted square-planar configuration. In both cases the ligand 1 spans trans positions with M-P bond lengths in the ranges of the literature data. Also the other bond distances fall in regular ranges. Ligand 1 has almost the same conformation in both complexes and is characterized by a strong out-of-plane deformation of the benzophenanthrene system as a consequence of severe overcrowding.

Introduction. -The bidentate ligand 2 , l l -bis (diphenylphosphinomethy1)benzo-[clphenanthrene (1) easily forms mononuclear square-planar complexes [MX2 (l)] and [MX(CO)(l)], where M is a d8 transition metal ion (M=Pd(II), Pt(I1) [2] or Rh (I), Ir (I) [ 11 and X is a halide ion). These complexes show electronic and NMR. features characteristic of the square-planar complexes of these metal ions with monodentate phosphine ligands in trans-positions.

As these complexes are being used as models for reactions related to homogeneous catalytic processes, it was of interest to establish the detailed features of their molecular structures.

📜 SIMILAR VOLUMES

Transition Metal Complexes with Bidentat
Transition Metal Complexes with Bidentate Ligands Spanning trans-Positions. VII. The preparation of the five-coordinate complexes [M(CO)3(1)] (M = Fe, Ru; (1) = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene)
✍ Rolf Holderegger; Luigi M. Venanzi 📂 Article 📅 1979 🏛 John Wiley and Sons 🌐 German ⚖ 292 KB 👁 1 views

## Abstract The five‐coordinate mononuclear complexes [M(CO)~3~(**1**)] (M = Fe, Ru; (**1**) = 2,11‐bis(diphenylphosphinomethyl)benzo[c]phenanthrene) have been prepared and assigned trigonal bipyramidal structures with apical phosphorus atoms from IR. and NMR. data.

Transition-Metal Complexes with Bidentat
Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. II. Preparation and properties of complexes trans-[MX2(1)] (M = Ni, Pd and Pt; X = Cl, Br and I; 1 = 2, 11-Bis(diphenylphosphinomethyl)benzo[c]phenanthrene)
✍ N. J. Destefano; D. K. Johnson; L. M. Venanzi 📂 Article 📅 1976 🏛 John Wiley and Sons 🌐 German ⚖ 472 KB 👁 1 views

It is shown that the ligand 2,ll-bis(diphenylphosphinomethyl)benzo[c]phenanthrene (1) reacts with nickel(II), palladium(I1) and platinum(l1) substrates giving either exclusively, or predominantly, mononuclear complexes of the type trans-[MXz (l)] in which the organic ligand spans trans-positions. It

Transition metal complexes with bidentat
Transition metal complexes with bidentate ligands spanning trans-positions. VI. The preparation of some diaryl- and dialkyl derivatives of 2,11-bis (phosphinomethyl)benzo [c]phenanthrene
✍ Pramesh N. Kapoor; Luigi M. Venanzi 📂 Article 📅 1977 🏛 John Wiley and Sons 🌐 German ⚖ 364 KB 👁 1 views

## Abstract The preparation of the ditertiary phosphines 2,11‐bis (di‐__m__‐tolylphosphinomethyl)benzo [__c__]phenanthrene (**1b**), 2,11‐bis (di‐__p__‐anisylphosphinomethyl)benzo‐[__c__]phenanthrene (**1c**), 2,11‐bis (di‐__m__‐trifluoromethylphenylphosphinomethyl) benzo‐[__c__]phenanthrene (**1d*

Transition-metal complexes with bidentat
Transition-metal complexes with bidentate ligands spanning trans-positions. Part XVIII. Crystal and molecular structure of the ligands 2,11-bis(di-R-phosphinomethyl)benzo[c]phenanthrene (R = Phenyl, tert-Butyl) and a comparison of their conformation in a variety of complexes
✍ Hans-Beat Bürgi; Judith Murray-Rust; Mercedes Camalli; Francesco Caruso; Luigi M 📂 Article 📅 1989 🏛 John Wiley and Sons 🌐 German ⚖ 439 KB 👁 1 views

The X-ray crystal structures of 2,1l-bis(di-R-phosphinomethyl)benzo[c]phenanthrenes (R = Ph, t -Bu) are reported. Both ligands have the same conformation and the substitution of a Ph by a t -Bu group does not cause significant changes in the tetracyclic aromatic unit which shows the same distortions

Transition metal complexes with bidentat
Transition metal complexes with bidentate ligands spanning trans-positions. XII. The preparation and properties of complexes trans-[MX2 (1)] and trans-[PtHCl (1)] (M = Ni, Pd and Pt; X = Cl and NCS; 1 = ditertiary phosphine)
✍ Pramesh N. Kapoor; Paul S. Pregosin; Luigi M. Venanzi 📂 Article 📅 1982 🏛 John Wiley and Sons 🌐 German ⚖ 394 KB 👁 1 views

## Abstract Complexes [MX~2~(1)] (M = Ni, Pd and Pt; X=Cl and NCS; 1 = 2,11‐bis(dialkyl‐[or diaryl]phosphinomethyl)benzo[__c__]phenanthrene; alkyl = cyclohexyl __t__‐butyl; aryl = __m__‐tolyl, __p__‐anisyl and __m__‐CF~3~ C~6~H~4~) have been synthesized. An NMR. study of the t‐butyl complexes prov