Gold(I) and Silver(I) Complexes of Diphosphacyclobutadiene Cobaltate Sandwich Anions |
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| Authors: | Jennifer Malberg Thomas Wiegand Prof?Dr Hellmut Eckert Dr Michael Bodensteiner Prof?Dr Robert Wolf |
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| Institution: | 1. Institute of Inorganic Chemistry, University of Regensburg, Universit?tsstrasse 31, 93040 Regensburg (Germany), Fax: (+49)?941 814485;2. Institute of Inorganic and Analytical Chemistry, WWU Münster, Corrensstrasse 30, 41849 Münster (Germany);3. Institute of Physical Chemistry and Graduate School of Chemistry, WWU Münster, Corrensstrasse 30, 41849 Münster (Germany), Fax: (+49)?251 83‐29159 |
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| Abstract: | The synthesis and structural characterization of the first coordination compounds of bis(diphosphacyclobutadiene) cobaltate anions M(P2C2R2)2]? is described. Reactions of the new potassium salts K(thf)3{Co(η4‐P2C2tPent2)2}] ( 1 ) and K(thf)4{Co(η4‐P2C2Ad2)2}] ( 2 ) with AuCl(tht)] (tht=tetrahydrothiophene), AuCl(PPh3)] and AgSbF6] afforded the complexes Au{Co(P2C2tPent2)2}(PMe3)2] ( 3 ), Au{Co(P2C2Ad2)2}]x ( 4 ), Ag{Co(P2C2Ad2)2}]x ( 5 ), Au(PMe3)4]Au{Co(P2C2Ad2)2}2] ( 6 ), K(18]crown‐6)(thf)2]Au{Co(P2C2Ad2)2}2] ( 7 ), and K(18]crown‐6)(thf)2]M{Co(P2C2Ad2)2}2] ( 8 : M=Au 9 : M=Ag) in moderate yields. The molecular structures of 2 and 3 , and 6 – 9 were elucidated by X‐ray crystallography. Complexes 4 – 9 were thoroughly characterized by 31P and 13C solid state NMR spectroscopy. The complexes Au{Co(P2C2Ad2)2}]x ( 4 ) and Ag{Co(P2C2Ad2)2}]x ( 5 ) exist as coordination polymers in the solid state. The linking mode between the monomeric units in the polymers is deduced. The soluble complexes 1 – 3 , 6 , and 7 were studied by multinuclear 1H‐, 31P{1H}‐, and 13C{1H} NMR spectroscopy in solution. Variable temperature NMR measurements of 3 and 6 in deuterated THF reveal the formation of equilibria between the ionic species Au(PMe3)4]+, Au(PMe3)2]+, Co(P2C2R2)2]?, and Au{Co(P2C2R2)2}2]? (R=tPent and Ad). |
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| Keywords: | cobalt gold phosphorus sandwich complexes silver solid‐state NMR spectroscopy |
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