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PREPARATION AND CO-ORDINATION PROPERTIES OF TRANS-CHLORO-BIS(TRIPHENYLPHOSPHINE)-PLATINIUM. CRYSTAL AND MOLECULAR STRUCTURE OF THE IONIC COMPOUND

DOI: 10.1039/DT9840002223

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2223 - 2232 (1984)

Update date:2022-08-03

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Authors:

Mantovani, AntonioMantovani, Antonio

Pelloso, MarioPelloso, Mario

Bandoli, GiulianoBandoli, Giuliano

Crociani, BrunoCrociani, Bruno

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Article abstract of DOI:10.1039/DT9840002223

The 1,2-bis(imino)propyl complex trans- can be prepared by the condensation reaction of monometylamine with the carbonyl group of (1).Complex (2) reacts with MCl2 and to give the adducts (3) (M=Cu,Zn, or Pt, and with chloro-bridged dimers in the presence of NaClO4 (molar ratio Pt:M'=1:1) to give the cationic complexes or .In the binuclear complexes (3) and (4) the 1,2-bis(imino)-propyl group of (2) is ?:?'-N,N'-chelated to the metal centres M and M' respectively.The reaction of (2) with (molar ratio Pt:M'=1:2) yields the (5), which are characterized in solution by conductivity measurements and 1H and 31P n.m.r. spectroscopy.The 1H n.m.r. data indicate an interaction between the cationic and the anionic species of (5) which involves breaking of one of the M'-Nimino bonds in the binuclear cation, without exchange of PPh3 and chloride ligands between the Pt and M' metal centres.When M'L2= Rh(CO)2, the reaction affords the complex (5c) as a red-brown microcrystalline product, which is partially associated in solution.The crystal and molecular structure of (5c) has been determined by X-ray diffraction analysis.Crystals are monoclinic, space group P21/a, with a=19.521(3), b=17.212(7), c=15.910(3) angstroem, β=104.11(2) deg, and Z=4.The structure has been determined by the heavy-atom method and refined to the conventional R of 0.055 for 3892 counter reflections (up to 2θ=43 deg, Mo-Kα radiation).The structure consist of discrete, well separated cationic binuclear species and distorted square-planar cis-(1-) anions.In the cation the rhodium co-ordinatio plane forms a dihdral angle of 81 deg with the platinium co-ordination plane, with bond distances in the normal range ( mean values: Rh-Cl 2.342, Pt-P 2.330, Rh-N 2.07, Rh-CO 1.81, Pt-Cl 2.375, Pt-C(sp2) 1.97 angstroem).In the solid state there are no unusually short intermolecular contacts.

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