trans-(Dimethyl sulfoxide-O)(dimethyl sulfoxide-S)bis(trifluoroacetato)palladium(II); alternative ligation modes of an ambidentate ligand

Bancroft, Daniel P.; Cotton, F. Albert; Verbruggen, M.

doi:10.1107/s0108270189001459

Cited by 32 publications

(28 citation statements)

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“…35 Interestingly, the molecular structures of both cis - and trans -[Pd(TFA) 2 ( S -DMSO)( O -DMSO)] have been reported, wherein DMSO is shown to reveal linkage isomerism. 36,37…”

Section: Resultsmentioning

confidence: 99%

Critical Role of Anions in Platinum(II) Precursors upon the Structural Motifs of Six-Membered Cycloplatinated N,N′,N″-Triarylguanidines

Mishra

Thirupathi

2018

ACS Omega

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The reactions of cis -[Pt(OAc) 2 (DMSO) 2 ] with 2 equiv of sym N , N ′, N ″-triarylguanidines, [ArN=C(NHAr) 2 ], in toluene under reflux condition for 8 h afforded six-membered cycloplatinated guanidines, [Pt{κ 2 ( C , N )}(OAc){κ 1 N (ArN=C(NHAr) 2 )}] [ sym = symmetrical; Ar = 2-MeC 6 H 4 ( 1 ) and 2,4-Me 2 C 6 H 3 ( 2 )], in 82 and 84% yields, respectively. The salt metathesis reaction of 1 with 1 equiv of AgTFA in CH 2 Cl 2 at room temperature (RT) afforded [Pt{κ 2 ( C , N )}(TFA){κ 1 N (ArN=C(NHAr) 2 )}] ( 3 ) in 94% yield. The reaction of cis -[Pt(TFA) 2 (DMSO) 2 ] with 1 equiv of [ArN=C(NHAr) 2 ] in toluene under reflux condition for 8 h afforded six-membered cycloplatinated guanidines, [Pt{κ 2 ( C , N )}(TFA)(DMSO)] [Ar = 2-MeC 6 H 4 ( 4 ), 4-MeC 6 H 4 ( 5 ), 2,4-Me 2 C 6 H 3 ( 6 ), and 2-(MeO)C 6 H 4 ( 7 )], in ≥73% yields. The reaction of trans -[PtCl 2 (PhCN) 2 ] with 2 equiv of [ArN=C(NHAr) 2 ] in toluene under reflux condition for 48 h afforded trans -[PtCl 2 {ArN=C(NHAr) 2 } 2 ] [Ar = 2-MeC 6 H 4 ( 8 ) and 2,4-Me 2 C 6 H 3 ( 9 )] in 90 and 45% yields, respectively. Complexes 8 and 9 were separately refluxed in MeOH for 8 h to afford six-membered cycloplatinated guanidines, [Pt{κ 2 ( C , N )}(μ-Cl)] 2 ( 10 and 11 ), in 93 and 96% yields, respectively, with concomitant formation of the respective guanidinium salts, [(ArNH) 3 ...

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“…35 Interestingly, the molecular structures of both cis - and trans -[Pd(TFA) 2 ( S -DMSO)( O -DMSO)] have been reported, wherein DMSO is shown to reveal linkage isomerism. 36,37…”

Section: Resultsmentioning

confidence: 99%

Critical Role of Anions in Platinum(II) Precursors upon the Structural Motifs of Six-Membered Cycloplatinated N,N′,N″-Triarylguanidines

Mishra

Thirupathi

2018

ACS Omega

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“…of DMSO in EtOAc, and X-ray diffraction analysis established the structure of trans- Pd( S -DMSO)( O -DMSO)(TFA) 2 (Figure 1), which exhibits only slight variations relative to the structure originally reported by Cotton and workers. 17 The S -bound DMSO ligand has a shorter S–O bond [1.4633(17) Å] and the O -bound DMSO ligand has a longer S–O bond [1.5509(16) Å] relative to that of free DMSO (1.52 Å 18 ). The solid-state infrared absorption spectrum of this complex reveals absorption bands at 1149 cm −1 and 923 cm −1 .…”

Section: Resultsmentioning

confidence: 99%

Characterization of DMSO Coordination to Palladium(II) in Solution and Insights into the Aerobic Oxidation Catalyst, Pd(DMSO)₂(TFA)₂

et al. 2012

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Recent studies have shown that Pd(DMSO)2(TFA)2 (TFA = trifluoroacetate) is an effective catalyst for a number of different aerobic oxidation reactions. Here, we provide insights into the coordination properties of DMSO to palladium(II) in both the solid state and in solution. A crystal structure of Pd(DMSO)2(TFA)2 confirms that the solid-state structure of this species has one O-bound and one S-bound DMSO ligand, and a crystallographically characterized mono-DMSO complex, trans-Pd(DMSO)(OH2)(TFA)2, exhibits an S-bound DMSO ligand. 1H and 19F NMR spectroscopic studies show that, in EtOAc and THF-d8, Pd(DMSO)2(TFA)2 consists of an equilibrium mixture of Pd(S-DMSO)(O-DMSO)(TFA)2 and Pd(S-DMSO)2(TFA)2. The O-bound DMSO is determined to be more labile than the S-bound DMSO ligand, and both DMSO ligands are more labile in THF relative to EtOAc as the solvent. DMSO coordination to PdII is substantially less favorable when the TFA ligands are replaced with acetate. An analogous carboxylate ligand effect is observed in the coordination of PdII to the bidentate sulfoxide ligand, 1,2-bis(phenylsulfinyl)ethane. DMSO coordination to Pd(TFA)2 is shown to be incomplete in AcOH-d4 and toluene-d8, resulting in PdII/DMSO adducts with < 2:1 DMSO:PdII stoichiometry. Collectively, these results provide useful insights into the coordination properties of DMSO to PdII under catalytically relevant conditions.

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“…[11,14] These observations are consistent with earlier studies of the coordination of dimethyl sulfoxide to palladium(II). [15,16] As we have previously speculated, [13] the ability of dimethyl sulfoxide to serve as a "hard" (O) or "soft" (S) ligand could play an important role in the interconversion between the relatively hard and soft Pd II and Pd 0 redox states during the catalytic cycle. Variabletemperature 1 H NMR spectroscopic analysis (À60 to 40 8C) revealed the coalescence of dimethyl sulfoxide ligand resonances, the O-bound dimethyl sulfoxide resonances at À40 8C, and the S-bound resonances at + 40 8C.…”

Section: Richard I Mcdonald and Shannon S Stahl*mentioning

confidence: 99%

Modular Synthesis of 1,2‐Diamine Derivatives by Palladium‐Catalyzed Aerobic Oxidative Cyclization of Allylic Sulfamides

2010

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Allylic sulfamides undergo efficient aerobic oxidative cyclization at room temperature, mediated by a new Pd catalyst system consisting of 5% Pd(TFA)2/10% DMSO in THF. The synthetic utility of these reactions is enhanced by several features: (1) the sulfamide substrates are accessible in multi-gram scale from the corresponding allylic and primary amines, (2) the cyclic sulfamide products are readily converted to the corresponding 1,2-diamines upon treatment with LiAlH4, and (3) substrates derived from chiral allylic amines cyclize with very high levels of diastereoselectivity.

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trans-(Dimethyl sulfoxide-O)(dimethyl sulfoxide-S)bis(trifluoroacetato)palladium(II); alternative ligation modes of an ambidentate ligand

Cited by 32 publications

References 0 publications

Critical Role of Anions in Platinum(II) Precursors upon the Structural Motifs of Six-Membered Cycloplatinated N,N′,N″-Triarylguanidines

Critical Role of Anions in Platinum(II) Precursors upon the Structural Motifs of Six-Membered Cycloplatinated N,N′,N″-Triarylguanidines

Characterization of DMSO Coordination to Palladium(II) in Solution and Insights into the Aerobic Oxidation Catalyst, Pd(DMSO)₂(TFA)₂

Modular Synthesis of 1,2‐Diamine Derivatives by Palladium‐Catalyzed Aerobic Oxidative Cyclization of Allylic Sulfamides

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trans-(Dimethyl sulfoxide-O)(dimethyl sulfoxide-S)bis(trifluoroacetato)palladium(II); alternative ligation modes of an ambidentate ligand

Cited by 32 publications

References 0 publications

Critical Role of Anions in Platinum(II) Precursors upon the Structural Motifs of Six-Membered Cycloplatinated N,N′,N″-Triarylguanidines

Critical Role of Anions in Platinum(II) Precursors upon the Structural Motifs of Six-Membered Cycloplatinated N,N′,N″-Triarylguanidines

Characterization of DMSO Coordination to Palladium(II) in Solution and Insights into the Aerobic Oxidation Catalyst, Pd(DMSO)2(TFA)2

Modular Synthesis of 1,2‐Diamine Derivatives by Palladium‐Catalyzed Aerobic Oxidative Cyclization of Allylic Sulfamides

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Characterization of DMSO Coordination to Palladium(II) in Solution and Insights into the Aerobic Oxidation Catalyst, Pd(DMSO)₂(TFA)₂