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Complexation Studies with a Calix[4]arene‐Derived Phosphinite − Divergent Arrays of Cavities Linked by MCl 2 Fragments (M = Pd, Pt)
Author(s) -
Faidherbe Pascale,
Wieser Catherine,
Matt Dominique,
Harriman Anthony,
De Cian André,
Fischer Jean
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199804)1998:4<451::aid-ejic451>3.0.co;2-p
Subject(s) - chemistry , phosphinite , triclinic crystal system , tetrahydrothiophene , calixarene , tetrahydrofuran , steric effects , molecule , palladium , aryl , crystallography , stereochemistry , yield (engineering) , methylenedioxy , crystal structure , halogen , catalysis , organic chemistry , alkyl , materials science , solvent , metallurgy
A cone‐shaped calix[4]arene‐derived monophosphinite, 25,27‐di(ethoxycarbonylmethoxy)‐26‐hydroxy‐28‐(diphenylphosphinooxy)calix[4]arene ( L 1 ), has been prepared in two steps from calix[4]arene. Treatment of L 1 with [AuCl(tetrahydrothiophene)] in tetrahydrofuran gave the phosphinite complex [AuCl L 1 ] ( 1 ). Reaction of [PdCl 2 (PhCN) 2 ] with two equivalents of L 1 gave selectively trans ‐[PdCl 2 L 1 2 ] ( 2 ). Complex 2 · 2 CH 2 Cl 2 crystallizes in the triclinic space group P 1¯. The molecule is centrosymmetric, leading to a divergent array of the two calixarene moieties. The palladium atom resides outside both cones. As a result of steric interactions, the meta and para carbon atoms of the PPh 2 ‐bearing aryl ring are significantly pushed to the interior of the cavity. The related platinum complex trans ‐[PtCl 2 L 1 2 2 ] ( 3 ), was obtained similarly from [PtCl 2 (PhCN) 2 ] and presents in the solid state a structure which is isomorphous to that of 2 . The diphosphinite 25,27‐di(ethoxycarbonylmethoxy)‐26,28‐bis(diphenylphosphinoxy)calix[4]arene (cone) ( L 2 ) has also been prepared and reacts with [PtCl 2 (PhCN) 2 ] to yield oligomeric material.