In:
Zeitschrift für anorganische und allgemeine Chemie, Wiley, Vol. 621, No. 11 ( 1995-11), p. 1832-1843
Abstract:
Chemistry of Polyfunctional Molecules. 118. Syntheses and Crystal Structures of Bicyclic Metallaphosphazenes with Four and Six Membered Rings Anhydrous MCl 2 (M = Pt, Fe) react with LiN(PPh 2 ) 2 ( 1 ) in the molar ratio of 1:2 in boiling toluene within 25 hours under partially oxidative scrambling of the PNP chain in 1 yielding the bicyclic metallaphosphazenes 5 a, b . magnified image While compound 5 a can be isolated in substance, the intermediate 5 b proves to be highly reactive but can be stabilized in the presence of CO, forming the 18‐valence‐electron coordination compound equation image as an isomeric trans( 6 a )/cis( 6 b ) mixture in the molar ratio of 99:1. Also treatment of anhydrous PtCl 4 with four equivalents of 1 in boiling toluene during 60 hours yields 5 a . Alkylation of 5 a with CH 3 I leads to the formation of the ionic species [Pt 2+ {Ph 2 PN(CH 3 )PPh 2 }(Ph 2 PN = PPh 2 = NPPh 2 − )]I − ( 9 ). The X‐ray crystal structures of 5 a × 1 CH 2 Cl 2 and 6 a reveal, that the metal centres have a planar P‐coordination polyhedron in the solid state. In the complex 9 × 2,5 CH 2 Cl 2 however the torsion angle between the PPtP planes of the four and six membered rings shows to be 15°. The six membered metallacycles in 5 a × 1 CH 2 Cl 2 , 6 a and 9 × 2,5 CH 2 Cl 2 differ in their geometrical arrangement. All the new compounds have also been characterized by their 1 H, 31 P{ 1 H}, 13 C{ 1 H} NMR, IR, Raman and mass spectra.
Type of Medium:
Online Resource
ISSN:
0044-2313
,
1521-3749
DOI:
10.1002/zaac.v621:11
DOI:
10.1002/zaac.19956211104
Language:
English
Publisher:
Wiley
Publication Date:
1995
detail.hit.zdb_id:
201094-X
detail.hit.zdb_id:
1481139-X
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