Heteroleptic κ2(N,C2)-2-phenylpyridine platinum complexes: The use of bis(pyrazolyl)borates as ancillary ligands

1H, 13C, 15N and 195Pt NMR studies of Au(III) and Pt(II) chloride organometallics with 2‐phenylpyridine

“…The significance of this factor for 2ppy * organometallics is well illustrated by the comparison of several corresponding Pt(II) and Pd(II) species, for which the H(6) * coord values noticeably increase with the platinide atomic mass (Table S4 [22] trans(N,N) [9] as well as in [Pt(2ppy * )(2ppy)X] (X = Cl, Br, I, SCN, ONO 2 , NO 2 : δ H(3 ) * = 6.05-6.29 ppm). [19] Similar or even smaller values were described for [Pt(3-hexyloxy-2ppy * )(3-hexyloxy-2ppy)Cl] (δ H(3 ) * = 6.30 ppm); [18] [Pt(2-(4-methylphenyl)-py * )(2-(4-methylphenyl)-py)Cl] (δ H(3 ) * = 6.19 ppm); [19] [17] [Pt(2-(2,4-difluorophenyl)-py * )(2-(2,4-difluorophenyl)-py)Cl] (δ H(3 ) * = 5.62 ppm). [48] This phenomenon seems to be caused mainly by the anisotropic influence of an additional azine molecule because, upon its absence, the δ H(3 ) * values were much larger (e.g.…”

“…[40] The same dependency can be found (Table S3, Supporting Information) for [Pt(3-hexyloxy-2ppy * )(3-hexyloxy-2ppy)Cl] ( H(6) * coord = 1.05 ppm versus H(6) coord = 0.50 ppm), [18] [Pt(2-(4-methylphenyl)-py * )(2-(4-methylphenyl)-py)Cl] ( H(6) * coord = 0.93 ppm versus H(6) coord = 0.58 ppm), [19] [Pt(2-(4-methoxyphenyl)-py * )(2-(4-methoxyphenyl)-py)Cl] ( H(6) * coord = 0.74 ppm versus H(6) coord = 0.44 ppm), [17] [5,9,17,20,21] H(6) * coord = 1.22 ppm for [Pt(2ppy * )(P(C 6 H 5 ) 3 )Cl]; [22] H(6) * coord = 0.73-0.79 ppm for [Pt(2ppy * )(CN) 2 ] − . [14,23] In contrast, when chlorides were absent, the coordination effects were of variable sign and magnitude: [26 -28] H(6) * coord = −0.56 ppm for [Pt(2ppy * ) (P(C 6 H 5 ) 3 )(CH 3 )]; [29] H(6) * coord = 1.00-1.12 ppm for trans…”

“…[40] Gaussian03 [42] software installed at the supercomputing centre in Torun (Poland) was used. [1] but entirely different from the suggestions of Fan et al [3] or Parish et al [15] The presence of eight proton signals corresponds well to the results of single-crystal X-ray studies for solid [Au(2ppy * )Cl 2 ] (IJAQEP [3] ), suggesting the preservation of its structure in DMSOd 6 [18] Fukuda et al (in CDCl 3 ): 9.62-H(6) * ( 3 J HPt = 18 Hz), 9.24-H(6) ( 3 J HPt = 20 Hz), 6.19-H(3 ) * ( 3 J HPt = 16 Hz). [19] c Formed in situ by dissolving [Pt(2ppy…”

“…[43 -46] The other pyridine protons in [Au(2ppy 3 or CD 2 Cl 2 , especially in case of the two high-frequency signals (9.50-9.62 and 9.15-9.24 ppm) and the one at the lowest frequency (6.10-6.20 ppm); [2,5,9,17 -19] they were already assigned by Niedermair, Mdleleni and Fukuda et al as H (6) * , H(6) and H(3 ) * , respectively [5,18,19] (see footnote (b) under Table 1). We have found the following order of 1 H peaks, based on the 1 H-13 C and 1 H-15 N HSQC or HMBC spectra :…”

“…In consequence, we have detected 11 signals for [Au(2ppy * )Cl 2 ] and (N,N)-[Pt(2ppy * )(2ppy)Cl] (11 for 2ppy * and 9 for 2ppy). Although their chemical shifts were already reported, they were never assigned [3,9,15,17,18] (Table 2).…”