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A Comparative Study of Cyclometallated Palladium(II) Compounds with Terdentate [C,N,S] Pincer Ligands − Crystal and Molecular Structure of [Pd{4‐MeC 6 H 3 C(Me)=NNC(=S)NHMe}(PPh 3 )] and [Pd{4‐MeOC 6 H 3 C(H)=N[2‐(SMe)C 6 H 4 ]}(Cl)]
Author(s) -
Amoedo Adriana,
Graña María,
Martínez Javier,
Pereira Teresa,
LópezTorres Margarita,
Fernández Alberto,
Fernández Jesús J.,
Vila José M.
Publication year - 2002
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 - 10.1002/1099-0682(200203)2002:3<613::aid-ejic613>3.0.co;2-a
Subject(s) - chemistry , pincer movement , palladium , deprotonation , medicinal chemistry , nucleophile , stereochemistry , crystal structure , ligand (biochemistry) , transmetalation , catalysis , crystallography , organic chemistry , ion , biochemistry , receptor
Treatment of the thiosemicarbazone ligands 4‐MeC 6 H 4 C(Me)=NN(H)C(=S)NHMe ( a ), 4‐MeC 6 H 4 C(Me)=NN(H)C(=S)NHEt ( b ), and 4‐MeC 6 H 4 C(Me)=NN(H)C(=S)NHPh ( c ) with K 2 [PdCl 4 ] produced the tetranuclear palladium(II) compounds [Pd{4‐MeC 6 H 3 C(Me)=NNC(=S)NHMe}] 4 ( 1a ), [Pd{4‐MeC 6 H 3 C(Me)=NNC(=S)NHEt}] 4 ( 1b ), and [Pd{4‐MeC 6 H 3 C(Me)=NNC(=S)NHPh}] 4 ( 1c ) with deprotonation of the NH group. Treatment of thiosemicarbazones 4‐MeOC 6 H 4 C(H)=NN(Me)C(=S)NH 2 ( d ) and 3‐MeOC 6 H 4 C(H)=NN(Me)C(=S)NH 2 ( e ) with K 2 [PdCl 4 ] gave the mononuclear palladium(II) compounds [Pd{4‐MeOC 6 H 3 C(H)=NN(Me)C(=S)NH 2 }(Cl)] ( 1d ) and [Pd{3‐MeOC 6 H 3 C(H)=NN(Me)C(=S)NH 2 }(Cl)] ( 1e ). Treatment of the Schiff base 4‐MeOC 6 H 4 C(H)=N[2‐(SMe)C 6 H 4 ] ( f ) with Li 2 [PdCl 4 ] afforded [Pd{4‐MeOC 6 H 3 C(H)=N[2‐(SMe)C 6 H 4 ]}(Cl)] ( 1f ). All the ligands are terdentate through the [C,N,S] atoms and the Pd−S bond formed is sufficiently strong to tolerate treatment with nucleophiles without bond cleavage. Treatment of 1a , 1b , and 1c with triphenylphosphane gave the mononuclear species 2a , 2b , and 2c , which upon treatment with hydrochloric acid resulted in the 1:1 electrolytes 3a , 3b , and 3c , with NH and C=S groups. Coordination of PPh 3 to Pd in 1f was achieved by treatment of the compound with sodium perchlorate, followed by the nucleophile in a 1:1 molar ratio, to yield 2f . The crystal structures of compounds 2a and 1f are described.