The Influence of the Methyl Substituents at C² Carbon of Thiosemicarbazones {R¹R²C²=N³‐N²H‐C¹(=S)N¹H₂} on Bonding and Structures of Copper(I) Complexes

Abstract

Reaction of copper(I) halides with acetone thiosemicarbazone (Hactsc) and acetaldehyde thiosemicarbazone (Hmtsc) in CH 3 CN in the presence of PPh 3 has formed dimeric complexes of type, [Cu 2 (µ-X) 2 (η 1 -S-Htsc) 2 (Ph 3 P) 2 ] (Htsc: X; Hmtsc, Br, 1; I, 2; Hactsc, I, 3; Cl, 5), and a monomer, [CuBr((η 1 -S-Hactsc)(Ph 3 P) 2 (4). The complexes have been characterized using analytical data, spectroscopy and X-ray crystallography (1Ϫ4). The presence of methyl substituents at C 2 carbon of thiosemicarbazone seems to

The Methyl Group at C2 Carbon in {(2‐C4H3S)–C2(Me)=N–NH–C1(=S)NH2} Alters Iodide‐Bridging to Sulfur‐Bridging in Copper(I) Iodide Complexes

“…The central core of sulfur-bridged dimer [Cu 2 (µ-S-Hattsc) 2 (η 1 -I) 2 (Ph 3 P) 2 ]·2H 2 O (1) is a parallelogram [Cu-S, 2.3394(11), 2.4402(10) Å] with short Cu···Cu distance (3.135 Å) relative to that in iodo-bridged dimer 3 (3.351 Å) [11]. The other bond parameters are similar to literature trends [11][12][13][14][15]. The angles at copper atom (81.95°-120.54°) reveal a distorted tetrahedral arrangement around each copper atom (Figure 1).…”

“…Thiosemicarbazones (I), an important class of nitrogen-and sulfur donors, received considerable attention because of their structural diversity [1,2], variable-bonding modes [3], metallation properties [4], ion-sensing ability [5,6], extraction properties [7], and pharmacological applications [8][9][10]. From this laboratory, recently coordination chemistry of coinage metals (Cu I , Ag I ) with thiosemicarbazones, in the presence of Ph 3 P has been reported (Scheme 1) [3,[11][12][13][14][15][16]. It was noted that in case of copper(I) halides, for substituents R 1 = pyridyl, R 2 = H, mode A was observed for X = Cl, Br, and I.…”

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

“…However, if the substituent at C 2 has a donor atom, and engages in bonding, the additional bonding modes observed are, 3 -X, N 3 , S-chelation (XV), 4 -X, N 3 , S-chelation and S-bridging (XVI), and 4 -X, N 3 , S-chelation and X-bridging (XVI) (e.g. X = N, O) [12][13][14][15][16][17][18][19][20][21].…”

“…Similarly, Rh I , Pd II and Pt II [26] in ethanol. Copper(I) complexes have been generally prepared by the direct reaction of a copper(I) halide with a thiosemicarbazone in presence of PPh 3 as co-ligand [12][13][14][15][16][109][110][111][112][113][114], or by the treatment of [Cu(MeCN) 4 ]PF 6 with a ligand in the basic medium [31]. There is only one report of electrochemical method for the preparation of Cu I -thiosemicarbazone complexes [18].…”