Trinuclear Palladium(II) Complexes with 2-Hydroxy-4-methoxyacetophenoneN4-Dimethylthiosemicarbazone: Synthesis, Spectral Studies and Crystal Structure of a Tripalladium Complex

Structural Studies of a Copper(II) Complex with Inequivalent 2-Acetylpyridine 3-Piperidylthiosemicarbazonato Ligands and a Nickel(II) Complex with Different Modes of Coordination by the Two Thiosemicarbazonato Moieties of 1-Phenylglyoxal Bis{N(4)-diethylthiosemicarbazone}

“…The Ni1±N21±N22±C22±S2 leastsquares plane has greater deviation, 0.0206 A Ê than the Ni1±S1±C12±N12, 0.0004 A Ê , and two planes are at an angle of 4.1 (8)°further indicating that the coordination sphere is less planar than a 5-5-5 trichelate system. The deviations from the expected molecular structures for these two compounds along with others previously reported [9±11], may be an important consideration concerning this class of compounds biological activity.…”

Structural Studies of a Copper(II) Complex with Inequivalent 2-Acetylpyridine 3-Piperidylthiosemicarbazonato Ligands and a Nickel(II) Complex with Different Modes of Coordination by the Two Thiosemicarbazonato Moieties of 1-Phenylglyoxal Bis{N(4)-diethylthiosemicarbazone}

“…The Ni1±N21±N22±C22±S2 leastsquares plane has greater deviation, 0.0206 A Ê than the Ni1±S1±C12±N12, 0.0004 A Ê , and two planes are at an angle of 4.1 (8)°further indicating that the coordination sphere is less planar than a 5-5-5 trichelate system. The deviations from the expected molecular structures for these two compounds along with others previously reported [9±11], may be an important consideration concerning this class of compounds biological activity.…”

Activation of C–H bonds of thiosemicarbazones by transition metals: synthesis, structures and importance of cyclometallated compounds

“…Further, tetranuclear complexes 22, 26 and 27 suspended in acetone with ditertiary phosphines (dppm, vdpp, dppb, and Fc) yielded dinuclear complexes (39)(40)(41)(42)(43)(44) as well as mononuclear complexes with one pendant PPh 2 group in each case (45)(46)(47)(48). 102 Reaction of tetranuclear complex 28 with Ph 2 P-CH 2 -PPh 2 , in acetone also formed P,P-bridged dimer, {Pd(C,N,S-L 25 )} 2 (m-Ph 2 P-CH 2 -PPh 2 ) and attempt to crystallize in chloroform led to the formation of a N 3 , S-chelated complex, cis-[Pd(N 3 ,S-L 25 ) 2 ] with no metallation retained.…”

“…105,106 Reactions of tetranuclear complexes 99-102 with diphosphines in acetone in 1 : 2 molar ratio formed P,P-bridged dinuclear complexes, {Pd(C,N,S-L)} 2 (m-P,P-ligand) (P,Pligand is a diphosphine) (103-120), 105,106 and ligands, L [36][37][38] with dppm in 1 : 4 molar ratio in acetone yielded mononuclear 121-122 complexes. 106 The presence of two halogens in the phenyl ring (R 1 ) and with R 2 being methyl/ethyl gave ligands L [39][40] which on reaction with K 2 PdCl 4 in ethanol-water again formed tetranuclear complexes 123 and 124 with C,N,S-terdentate thio-ligands. 109 Tetranuclear complexes 123 and 124 with dppm in acetone formed mononuclear complexes 125 and 126 with one pendant -PPh 2 group in each case.…”

Bonding and structure trends of thiosemicarbazone derivatives of metals—An overview

“…1 -S, 2 -S, 2 -N 3 , S-chelation, 2 -N 3 , S-chelation and S-bridging, 3 -X, N 3 , S-chelation, 3 -X, N 3 , S-chelation-cum-S-bridging, 3 -X, N 3 , S-chelation and X-bridging [22][23][24][25][26][27][28][29]. In addition, 2 -N 2 , S (XVIII) and N 2 , S-bridging and Sbridging modes (XIX) are identified [30,31].…”

“…In the trinuclear complexes, [Pd 3 L 3 ]·DMSO 215 [28], and [Pd 3 L 3 ]·DMF 216 [243], the dinegative ligand coordinates to a Pd II center via O, N 3 , S-donor atoms forming a neutral repeat species Pd(O, N 3 , S), and three such species combine via S atoms to form trinuclear complexes, with the central six-membered Pd 3 S 3 ring adopting chair conformation (Chart 27). Tetranuclear complexes [Pd 4 L 4 ] 217 and 218 involve binding via C, N 3 , and S-donor atoms [103,244] and complex 219 binds via N 4 , N 3 , S-donor atoms [245].…”

Structural Studies of a Copper(II) Complex with Inequivalent 2-Acetylpyridine 3-Piperidylthiosemicarbazonato Ligands and a Nickel(II) Complex with Different Modes of Coordination by the Two Thiosemicarbazonato Moieties of 1-Phenylglyoxal Bis{N(4)-diethylthiosemicarbazone}

“…The Ni1±N21±N22±C22±S2 leastsquares plane has greater deviation, 0.0206 A Ê than the Ni1±S1±C12±N12, 0.0004 A Ê , and two planes are at an angle of 4.1 (8)°further indicating that the coordination sphere is less planar than a 5-5-5 trichelate system. The deviations from the expected molecular structures for these two compounds along with others previously reported [9±11], may be an important consideration concerning this class of compounds biological activity.…”

Activation of C–H bonds of thiosemicarbazones by transition metals: synthesis, structures and importance of cyclometallated compounds

“…Further, tetranuclear complexes 22, 26 and 27 suspended in acetone with ditertiary phosphines (dppm, vdpp, dppb, and Fc) yielded dinuclear complexes (39)(40)(41)(42)(43)(44) as well as mononuclear complexes with one pendant PPh 2 group in each case (45)(46)(47)(48). 102 Reaction of tetranuclear complex 28 with Ph 2 P-CH 2 -PPh 2 , in acetone also formed P,P-bridged dimer, {Pd(C,N,S-L 25 )} 2 (m-Ph 2 P-CH 2 -PPh 2 ) and attempt to crystallize in chloroform led to the formation of a N 3 , S-chelated complex, cis-[Pd(N 3 ,S-L 25 ) 2 ] with no metallation retained.…”

“…105,106 Reactions of tetranuclear complexes 99-102 with diphosphines in acetone in 1 : 2 molar ratio formed P,P-bridged dinuclear complexes, {Pd(C,N,S-L)} 2 (m-P,P-ligand) (P,Pligand is a diphosphine) (103-120), 105,106 and ligands, L [36][37][38] with dppm in 1 : 4 molar ratio in acetone yielded mononuclear 121-122 complexes. 106 The presence of two halogens in the phenyl ring (R 1 ) and with R 2 being methyl/ethyl gave ligands L [39][40] which on reaction with K 2 PdCl 4 in ethanol-water again formed tetranuclear complexes 123 and 124 with C,N,S-terdentate thio-ligands. 109 Tetranuclear complexes 123 and 124 with dppm in acetone formed mononuclear complexes 125 and 126 with one pendant -PPh 2 group in each case.…”

Bonding and structure trends of thiosemicarbazone derivatives of metals—An overview

“…1 -S, 2 -S, 2 -N 3 , S-chelation, 2 -N 3 , S-chelation and S-bridging, 3 -X, N 3 , S-chelation, 3 -X, N 3 , S-chelation-cum-S-bridging, 3 -X, N 3 , S-chelation and X-bridging [22][23][24][25][26][27][28][29]. In addition, 2 -N 2 , S (XVIII) and N 2 , S-bridging and Sbridging modes (XIX) are identified [30,31].…”

“…In the trinuclear complexes, [Pd 3 L 3 ]·DMSO 215 [28], and [Pd 3 L 3 ]·DMF 216 [243], the dinegative ligand coordinates to a Pd II center via O, N 3 , S-donor atoms forming a neutral repeat species Pd(O, N 3 , S), and three such species combine via S atoms to form trinuclear complexes, with the central six-membered Pd 3 S 3 ring adopting chair conformation (Chart 27). Tetranuclear complexes [Pd 4 L 4 ] 217 and 218 involve binding via C, N 3 , and S-donor atoms [103,244] and complex 219 binds via N 4 , N 3 , S-donor atoms [245].…”

Structural Studies of a Copper(II) Complex with Inequivalent 2-Acetylpyridine 3-Piperidylthiosemicarbazonato Ligands and a Nickel(II) Complex with Different Modes of Coordination by the Two Thiosemicarbazonato Moieties of 1-Phenylglyoxal Bis{N(4)-diethylthiosemicarbazone}

“…The Ni1±N21±N22±C22±S2 leastsquares plane has greater deviation, 0.0206 A Ê than the Ni1±S1±C12±N12, 0.0004 A Ê , and two planes are at an angle of 4.1 (8)°further indicating that the coordination sphere is less planar than a 5-5-5 trichelate system. The deviations from the expected molecular structures for these two compounds along with others previously reported [9±11], may be an important consideration concerning this class of compounds biological activity.…”

Activation of C–H bonds of thiosemicarbazones by transition metals: synthesis, structures and importance of cyclometallated compounds

“…Further, tetranuclear complexes 22, 26 and 27 suspended in acetone with ditertiary phosphines (dppm, vdpp, dppb, and Fc) yielded dinuclear complexes (39)(40)(41)(42)(43)(44) as well as mononuclear complexes with one pendant PPh 2 group in each case (45)(46)(47)(48). 102 Reaction of tetranuclear complex 28 with Ph 2 P-CH 2 -PPh 2 , in acetone also formed P,P-bridged dimer, {Pd(C,N,S-L 25 )} 2 (m-Ph 2 P-CH 2 -PPh 2 ) and attempt to crystallize in chloroform led to the formation of a N 3 , S-chelated complex, cis-[Pd(N 3 ,S-L 25 ) 2 ] with no metallation retained.…”

“…105,106 Reactions of tetranuclear complexes 99-102 with diphosphines in acetone in 1 : 2 molar ratio formed P,P-bridged dinuclear complexes, {Pd(C,N,S-L)} 2 (m-P,P-ligand) (P,Pligand is a diphosphine) (103-120), 105,106 and ligands, L [36][37][38] with dppm in 1 : 4 molar ratio in acetone yielded mononuclear 121-122 complexes. 106 The presence of two halogens in the phenyl ring (R 1 ) and with R 2 being methyl/ethyl gave ligands L [39][40] which on reaction with K 2 PdCl 4 in ethanol-water again formed tetranuclear complexes 123 and 124 with C,N,S-terdentate thio-ligands. 109 Tetranuclear complexes 123 and 124 with dppm in acetone formed mononuclear complexes 125 and 126 with one pendant -PPh 2 group in each case.…”

Bonding and structure trends of thiosemicarbazone derivatives of metals—An overview

“…1 -S, 2 -S, 2 -N 3 , S-chelation, 2 -N 3 , S-chelation and S-bridging, 3 -X, N 3 , S-chelation, 3 -X, N 3 , S-chelation-cum-S-bridging, 3 -X, N 3 , S-chelation and X-bridging [22][23][24][25][26][27][28][29]. In addition, 2 -N 2 , S (XVIII) and N 2 , S-bridging and Sbridging modes (XIX) are identified [30,31].…”

“…In the trinuclear complexes, [Pd 3 L 3 ]·DMSO 215 [28], and [Pd 3 L 3 ]·DMF 216 [243], the dinegative ligand coordinates to a Pd II center via O, N 3 , S-donor atoms forming a neutral repeat species Pd(O, N 3 , S), and three such species combine via S atoms to form trinuclear complexes, with the central six-membered Pd 3 S 3 ring adopting chair conformation (Chart 27). Tetranuclear complexes [Pd 4 L 4 ] 217 and 218 involve binding via C, N 3 , and S-donor atoms [103,244] and complex 219 binds via N 4 , N 3 , S-donor atoms [245].…”