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T‐Shaped Platinum Boryl Complexes: Synthesis and Structure
Author(s) -
Braunschweig Holger,
Radacki Krzysztof,
Uttinger Katharina
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800879
Subject(s) - platinum , chemistry , organic chemistry , catalysis
A series of cationic T‐shaped 14‐electron boryl complexes of the type trans ‐[(Cy 3 P) 2 Pt{B(X)X′}] + (X=Br; X′= ortho ‐tolyl, t Bu, NMe 2 , piperidyl, Br; XX′=(NMe 2 ) 2 , catecholato) were synthesized by halide abstraction from trans ‐[(Cy 3 P) 2 Pt(Br){B(X)X′}] (Cy=cyclohexyl) with Na[BAr f 4 ] (Ar f =3,5‐(CF 3 ) 2 C 6 H 3 ), K[B(C 6 F 5 ) 4 ], or Na[BPh 4 ]. X‐ray diffraction studies were performed on all compounds, revealing a subtle correlation between the trans ‐influence of the boryl moiety and the PtH and PtC separations. However, no notable agostic CH interaction with the platinum center was detected. trans ‐[(Cy 3 P) 2 Pt(BCat)] + (Cat=catecholato), the complex with the shortest PtH and PtC distances, was treated with Lewis bases (L), forming compounds of the type trans ‐[(Cy 3 P) 2 Pt(L)(BCat)] + , thus proving a decisive influence of the degree of trans ‐influence exerted by the boryl ligands on the chemical reactivity of the title complexes. Another point that was investigated and clarified is the different behavior of trans ‐[(Cy 3 P) 2 Pt(Br){B(Br)Mes}] (Mes=mesityl) towards K[B(C 6 F 5 ) 4 ] with formation of the borylene species trans ‐[(Cy 3 P) 2 Pt(Br)(BMes)] + .