Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

Abstract

Reactions of [Pt(SeC5H4N)2(P∩P)] with M(OAc)2.2H2O/MX2 (P∩P = dppm, dppp; M = Zn, Cd, Hg, Cu; X = Cl) resulted various products depend upon the nature of the phosphine. In case of dppm, reaction between [Pt(SeC5H4N)2(dppm)] and M(OAc)2.2H2O/MX2 (M = Zn, Cd, Hg) afforded an exchange product of composition [PtCl2(dppm)]. Similarly, the reaction with 'dppp' analog yielded an adduct [{Pt(SeC5H4N)2(dppp)}MX2] (M = Cd, Hg, Cu; X = Cl, OAc).Whereas, reaction with Zn(OAc)2, on extraction with dichloromethane resulted the product with the loss of one selenium atom of composition [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]. These complexes were characterized by elemental analyses and NMR ( 1 H, 31 P, 77 Se, 195 Pt) spectroscopy. The molecular structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] was established by single crystal X-ray diffraction analyses.

Ruthenium Complexes with N‐Bound 2‐Pyridonato Ligand as O‐Donors: A New Synthetic Approach and the Effect on Reactivity

“…Complex 1 and ligand L 1 were prepared according to literature procedure. [14,15] 1 H, 13 C{ 1 H}, 15 N and 119 Sn{ 1 H} NMR spectra were recorded on a Bruker Avance 400 and 500 MHz NMR spectrometer at 298 K. The 1 H and 13 C{ 1 H} NMR spectra were referenced internally to residual proton-solvent and solvent resonances, respectively, and are reported relative to Me 4 Si (δ = 0 ppm). Synthesis of [(η 6 -p-cymene)RuI(k 2 -L 1 )](I) (2).…”

“…1 H NMR (CDCl 3 , 400.13 MHz): δ (ppm) 0.74 (d, 3H, CH 3 CH(cym), 3 J( 1 H, 1 H) = 6.4 Hz), 0.98-1.02 (m, 6H, CH 3 CH(dipp), 1.15-1.17 (m, 6H, CH 3 CH(dipp), 1.38 (d, 3H, CH 3 CH(cym) 3 J( 1 H, 1 H) = 6.8 Hz ), 2.32 (s, 3H, CH 3 (cym)), 2.53 (sept, 1H, CH 3 CH(dipp), 3 J( 1 H, 1 H) = 6.8 Hz), 2.64 (sept, 1H, CH 3 CH(dipp), 3 J( 1 H, 1 H) = 6.8 Hz), 3.74 (sept, 1H, CH 3 CH-(cym), 3 J( 1 H, 1 H) = 6.4 Hz), 4.33 (s, 3H, CH 3 O), 4.70 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.0 Hz), 5.35 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.0 Hz), 5.57 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.7 Hz), 5.79 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.7 Hz), 7.21-7.34 (m, 3H, ArÀ H), 7.46 (d, 1H, ArÀ H, 3 J( 1 H, 1 H) = 8.4 Hz), 8.10-8.20 (m, 2H, ArÀ H), 8.49 (s, 1H, CH=N). 13 C{ 1 H} NMR (CDCl 3 , 100.613): δ (ppm) 20.9 (CH 3 (cym)), 21.5; 21.9; 23.3; 23.9; 26.0; 27.9 (CH 3 -iPr), 28.0; 29.4 (CH(dipp)), 31.9 (CH(cym)), 59.3 (CH 3 O), 82.9; 85.3; 87.4; 87.8 (Ar(cym)-C 2,3,5,6 ), 98.5; 109.7 (Ar(cym)-C 1,4 ), 111.8; 124.4; 124.8, 124.9; 129.5 (Ar-CH), 139.2; 141.7 (ArÀ C), 142.9 (Ar-CH), 148.6; 152.6 (ArÀ C), 166.9 (COMe), 170.5 (CH=N). 15 N NMR (CDCl 3 , 50.697 MHz): δ (ppm) À 110.3 (py); À 170.3 (imine).…”

“…(cym), 3 J( 1 H, 1 H) = 6.8 Hz), 1.38 (d, 3H, CH 3 CH(dipp), 3 J( 1 H, 1 H) = 6.8 Hz), 2.17 (s, 3H, CH 3 (cym)), 2.75 (sept, 1H, CH 3 CH(dipp), 3 J( 1 H, 1 H) = 6.8 Hz), 2.93 (sept, 1H, CH 3 CH(dipp), 3 J( 1 H, 1 H) = 6.8 Hz), 4.03 (sept, 1H, CH 3 CH(cym), 3 J( 1 H, 1 H) = 6.7 Hz), 4.85 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 5.7 Hz), 4.91 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 5.7 Hz), 5.29 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.2 Hz), 6.41 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.2 Hz), 6.49 (d, 1H, ArÀ H, 3 J( 1 H, 1 H) = 6.4 Hz), 6.61 (d, 1H, ArÀ H, 3 J( 1 H, 1 H) = 8.3 Hz), 7.20 (t, 1H, ArÀ H, 3 J( 1 H, 1 H) = 7.5 Hz), 7.23-7.26 (m, 2H, ArÀ H), 7.31 (d, 1H, ArÀ H, 3 J( 1 H, 1 H) = 7.7 Hz), 7.70 (s, 1H, CH=N). 13 C{ 1 H} NMR (CDCl 3 , 125.758): δ (ppm) 17.0 (CH 3 (cym)), 21.9; 24.9; 25.2; 26.0; 26.9; 29.1 (CH 3 -iPr), 30.0 (CH(dipp)) 30.7 (CH(cym)), 34.4 (CH(dipp)), 82.7; 88.2; 88.3; 88.7 (Ar(cym)-C 2,3,5,6 ), 102.2; 109.6 (Ar(cym)-C 1,4 ), 118.3; 126.4; 126.8; 127.4; 131.3; 138.5; 143.2; 146.0; 151.6; 155.0 (ArÀ C + C-py), 172.8 (C=O), 175.3 (CH=N). 15 N NMR (CDCl 3 , 50.697 MHz): δ (ppm) À 124.7 (py); À 182.1 (imine).…”

“…Hz ), 2.17 (s, 3H, CH 3 (cym)), 2.63 (sept, 1H, CH 3 CH(dipp), 3 J( 1 H, 1 H) = 6.7 Hz), 2.75 (sept, 1H, CH 3 CH(dipp), 3 J( 1 H, 1 H) = 6.7 Hz), 3.80 (sept, 1H, CH 3 CH-(cym), 3 J( 1 H, 1 H) = 6.7 Hz), 4.87 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 5.8 Hz), 5.03 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 5.8 Hz), 5.38 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.4 Hz), 6.09 (d, 1H, Ar(cym)-H, 3 J( 1 H, 1 H) = 6.4 Hz), 7.28 (d, 2H, ArÀ H, 3 J( 1 H, 1 H) = 8.0 Hz), 7.32-7.37 (m, 2H, ArÀ H), 7.68 (t, 1H, ArÀ H, 3 J( 1 H, 1 H) = 7.8 Hz), 8.10 (s, 1H, CH=N), 8.12 (d, 1H, ArÀ H, 3 J( 1 H, 1 H) = 8.6 Hz), 14,40 (s, 1H, H + ). 13 C{ 1 H} NMR (CDCl 3 , 100.613): δ (ppm) 13.9 (CH 3 (cym)), 16.7; 17.3; 17.9; 18.7; 20.4; 20.9 (CH 3 -iPr), 22.1; 22.6 (CH(dipp)), 22.8 (CH(cym)), 77.3; 80.0; 80.8; 80.9 (Ar(cym)-C 2,3,5,6 ), 96.2; 103.1 (Ar(cym)-C 1,4 ), 113.3; 116.9; 119.1; 119.7; 124.1 (Ar-CH), 134.5; 134.9 (ArÀ C), 137.3 (Ar-CH), 142.9; 146.1 (ArÀ C), 161.9 (COH), 166.1 (CH=N). 15 N NMR (CDCl 3 , 50.697 MHz): δ (ppm) À 117,0 (py); À 174,0 (imin).…”

“… [10] On the other hand, thio‐ and selenopyridonato ligands, heavier analogues of pyridonato ligand, allowed the straightforward preparation of the monomeric Pt−Cd or Pt−Hg bimetallic complexes (Figure 2). [11–13] …”