Palladium(II) and platinum(II) complexes of β-functionalized ethyl selenolates: Effect of substitution on synthesis, reactivity, spectroscopy, structures and thermal behavior

Kumbhare, Liladhar B.; Wadawale, Amey; Jain, Vimal K.; Kolay, Siddharth; Nethaji, Munirathinam

doi:10.1016/j.jorganchem.2009.08.005

Cited by 21 publications

(8 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The 13 C NMR spectrum of the latter displayed two sets of resonances for the pyridyl ring as has been reported for the hexanuclear homoleptic selenolates, [Pd(SeR) 2 ] 6 . 35 However, the 77 Se NMR spectrum showed a single resonance.…”

Section: Syntheses and Spectroscopymentioning

confidence: 97%

Syntheses of Pd(ii)/Pt(ii) complexes with non-chelating 4-pyridylselenolate ligand ranging from mononuclear to macrocyclic structures and their utility as catalysts in Suzuki C–C coupling reaction

et al. 2013

View full text Add to dashboard Cite

Treatment of Na2PdCl4 or [MCl2(PhCN)2] with bis(4-pyridyl)diselenide yielded an insoluble product of composition [MCl2(4,4′-(C5H4N)2Se2)]n (1). The reactions of Na2PdCl4 with one and two eq. of Na(4-SeC5H4N) afforded insoluble products [PdCl(4-SeC5H4N)]n (2) and [Pd(4-SeC5H4N)2]n (3), respectively. On treatment with PPh3, 2 and 3 gave trans-[PdCl(4-SeC5H4N)(PPh3)2] (4a) and trans-[Pd(4-SeC5H4N)2(PPh3)2] (5a), respectively. The oxidative addition of bis(4-pyridyl)diselenide to Pt(PPh3)4 exclusively yielded trans-[Pt(4-SeC5H4N)2(PPh3)2] (5b). The treatment of two eq. of Na(4-SeC5H4N) with cis-[PtX2(PR3)2] afforded 5b (X = Cl) and trans-[Pt(4-SeC5H4N)2(PEt3)2] (5c) (X = Cl or CF3SO3). The reactions of cis-[MCl2(P∩P)] and [M2Cl2(μ-Cl)2(PR3)2] with two eq. of Na(4-SeC5H4N) exclusively yielded cis-[M(4-SeC5H4N)2(P∩P)] (M/P∩P = Pd/dppe (6a), Pt/dppm (6b) and Pt/dppp (6c)) and [MCl(4-SeC5H4N)(PR3)]n (7), respectively. The complex trans-[PtCl(4-SeC5H4N)(PEt3)2] (4b) was isolated from the redistribution reaction between 5c and cis-[PtCl2(PEt3)2]. The complex [PdCl(4-SeC5H4N)(PPh3)]n (7b) exists in bi- and tri-nuclear forms, whereas [MCl(4-SeC5H4N)(PEt3)]n (7a, 7c) and [PtCl(4-SeC5H4N)(PMe2Ph)]n (7d) retain their trinuclear structure in solution. Molecular structures of 4a, 4b, 5a, 5c, 6a, 6c, 7a, 7b and 7c were established by single crystal X-ray diffraction analyses. The complexes trans-[PdCl(4-SeC5H4N)(PPh3)2] and [PdCl(4-SeC5H4N)(PPh3)]n can act as catalysts for Suzuki C–C cross coupling reaction.

show abstract

Section: Syntheses and Spectroscopymentioning

confidence: 97%

Syntheses of Pd(ii)/Pt(ii) complexes with non-chelating 4-pyridylselenolate ligand ranging from mononuclear to macrocyclic structures and their utility as catalysts in Suzuki C–C coupling reaction

et al. 2013

View full text Add to dashboard Cite

show abstract

“…The Pd-P distances are well in agreement with the reported values. 45,46 The Pd-Te distances (∼2.63 Å) are longer than those reported for palladium complexes containing non-bridging tellurolate ligands, e.g. [PdCl(TeCH 2 CH 2 CH 2 NMe 2 )(PR 3 )] (PR 3 = PPr 3 (Pd-Te = 2.5095(8) Å); PMePh 2 (Pd-Te = 2.5156(6) Å), 47 [PdCl{2-TeC 5 H 3 (3-Me)N}(PPh 3 )] (Pd-Te = 2.5606(8) Å), 33 but similar to those in other bridging systems, e.g.…”

Section: X-ray Crystallographymentioning

confidence: 99%

Reactivity of 2-chalcogenopyridines with palladium–phosphine complexes: isolation of different complexes depending on the nature of chalcogen atom and phosphine ligand

et al. 2013

Self Cite

View full text Add to dashboard Cite

Reactions of either Pd(0) phosphine complexes with dipyridyldichalcogenides or [PdCl2(P∩P)] (P∩P = dppe, dppp) with pyridylchalcogenolate ions have been examined and a variety of Pd(II) complexes have been isolated and characterized. Oxidative addition of {SeC5H3(3-R)N}2 (R = H or Me) to [Pd(P∩P)2] (P∩P = dppe, dppp) gave either a mononuclear complex, [Pd{2-Se-C5H3(3-R)N}2(P∩P)] (for P∩P/R: dppe/H or Me; dppp/H) or a cationic binuclear complex, [Pd2{μ-SeC5H3(3-Me)N}2(dppp)2]2+ (4b) (R = Me) whereas reactions involving the tellurium analogue exclusively afforded trinuclear complexes, [Pd3(μ-Te)2(P∩P)3]Cl2 (P∩P = dppe (2) or dppp (6)). The latter was also obtained in the substitution reaction between [PdCl2(P∩P)] and NaTeC5H3(3-R)N. The substitution reactions between [PdCl2(dppe)] and Pb{EC5H3(3-R)N}2 yielded mononuclear complexes, [Pd{2-E-C5H3(3-R)N}2(dppe)] (1a–1e) (E = S, Se or Te) while in the case of [PdCl2(dppp)], the reactions resulted in the formation of mono-, bi- and tri- nuclear complexes depending on the nature of the chalcogen atom (E = S, Se or Te) and the substituent on the pyridyl ring (R = H or Me). Treatment of dipyridyl ditellurides, {TeC5H3(3-R)N}2 (R = H or Me), with [Pd(PPh3)4] gave expected tellurolate complexes, [Pd{2-TeC5H3(3-R)N}2(PPh3)2] (7a, 7b) which on prolonged standing in CDCl3 solution gave green crystals of [PdCl{2-Te(Cl)2C5H3(3-Me)N}(PPh3)] (9). The molecular structures of {TeC5H3(3-Me)N}2, [Pd2{μ-TeC5H3(3-Me)N}2(dppp)2]Cl2·3H2O (5·3H2O), [Pd3(μ-Te)2(dppp)3]Cl2·3CHCl3 (6·3CHCl3) and [PdCl{2-Te(Cl)2C5H3(3-Me)N}(PPh3)] (9) were established by single crystal X-ray diffraction analyses.

show abstract

“…15,[18][19][20][21] Tiara-like nickel complexes have received considerable attention resulting in the preparation of complexes with a variety of ring sizes [Ni(-SR) 2 ] n (n = [4][5][6][8][9][10][11][12]. 15,[17][18][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] In contrast, although several tiara-like hexanuclear palladium complexes have been reported, 9,14,19,[36][37][38][39][40][41][42][43] only one octanuclear complex, i.e., [Pd(-S n Pr) 2 ] 8 , is known, and was obtained as a mixture with hexanuclear [Pd(-S n Pr) 2 ] 6 . 19 For platinum, infinite thiolates and selenolates [Pt(-ER) 2 ] ∞ (E = S, Se) have been synthesized using a solvothermal method; …”

Section: Introductionmentioning

confidence: 99%

Tiara-like Octanuclear Palladium(II) and Platinum(II) Thiolates and Their Inclusion Complexes with Dihalo- or Iodoalkanes

2014

View full text Add to dashboard Cite

A tiara-like octanuclear palladium thiolate complex, [Pd(-SCH 2 CO 2 Me) 2 ] 8 that has a toroidal structure, was synthesized via reactions of either PdCl 2 with methyl thioglycolate/N,N-diisopropylethylamine (DIEA) (conventional method) or [PdCl 2 (MeCN) 2 ] with m-C 6 H 4 (CMe 2 SCH 2 CO 2 Me) 2 (alternative method). In the latter method, the tiara-like complex formed via the corresponding SCS-pincer complex and/or 1:1 PdCl 2 and ligand complexes. With respect to the platinum analogs, the alternative method efficiently produced the tiara-like octanuclear complex, [Pt(-SCH 2 CO 2 Me) 2 ] 8 , in high purity. Small molecules, such as CH 2 Cl 2 , ClCH 2 CH 2 Cl, CH 2 Br 2 , and CH 3 I, were accommodated in the inner voids of the tiara rings to form 1:1 inclusion complexes. These complexes are stabilized by weak CH···X hydrogen bonds (X = Cl or Br) between the methylene protons of four or eight axially positioned methoxycarbonylmethyl groups on the tiara rings and the halogen atoms of the guest molecules, as well as weak coordination of the halogen atoms to the transition-metal atoms.2

show abstract

Palladium(II) and platinum(II) complexes of β-functionalized ethyl selenolates: Effect of substitution on synthesis, reactivity, spectroscopy, structures and thermal behavior

Cited by 21 publications

References 49 publications

Syntheses of Pd(ii)/Pt(ii) complexes with non-chelating 4-pyridylselenolate ligand ranging from mononuclear to macrocyclic structures and their utility as catalysts in Suzuki C–C coupling reaction

Syntheses of Pd(ii)/Pt(ii) complexes with non-chelating 4-pyridylselenolate ligand ranging from mononuclear to macrocyclic structures and their utility as catalysts in Suzuki C–C coupling reaction

Reactivity of 2-chalcogenopyridines with palladium–phosphine complexes: isolation of different complexes depending on the nature of chalcogen atom and phosphine ligand

Tiara-like Octanuclear Palladium(II) and Platinum(II) Thiolates and Their Inclusion Complexes with Dihalo- or Iodoalkanes

Contact Info

Product

Resources

About