Synthesis and reactivity of an 2-azabutadiene-based π-conjugated dithioether: Formation of a N,S-ligated molybdenum chelate complex and C,N,S-pincer complexes of palladium and platinum

Jacquot-Rousseau, Sandrine; Khatyr, Abderrahim; Schmitt, Gérard; Knorr, Michael; Kubicki, Marek M.; Blacque, Olivier

doi:10.1016/j.inoche.2005.03.016

Cited by 15 publications

(11 citation statements)

References 29 publications

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“…The reactivity of 1 towards the "thio" nucleophiles SPh, SCH 2 C(O)COEt (SGly) and SiPr [24] and OPh reported in this paper is quite different compared with that reported for the hard bases. Why in the X-ray structures are they found on the C3 atom of azadiene 1?…”

Section: Dft Calculationscontrasting

confidence: 79%

“…Furthermore, the easy preparation of 2a,b and 7 is a promising development in coordination chemistry. As communicated for the molybdenum complex cis-[(OC) 4 Mo{(iPrS) 2 -C=C(H)-N=CPh 2 }], [24] these ligand systems are prone to ligate to metal centres via the soft thioether function or the harder imine nitrogen atom. We are currently investigating the coordination chemistry of these ligands with other transition metals like rhenium, copper and mercury as well as the photophysical properties of these systems.…”

Section: Discussionmentioning

confidence: 99%

“…Note also that the values of these dihedral angles are 28.7(1)°in 1 (X = Cl) [19] and 38.8(3)°in 2a (X = SiPr). [24] The length of the C(2)-C(3) double bond in 7 …”

Section: Molecular Structures Of 2b Andmentioning

confidence: 99%

“…Part of this work, that concerning the iPrSsubstituted azadiene 2a, has recently appeared in a preliminary communication. [24] Results and Discussion…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation

et al. 2006

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Treatment of 4,4‐dichloro‐1,1‐diphenyl‐2‐azabuta‐1,3‐diene [Cl2C=C(H)‐N=CPh2] (1) with excess sodium isopropylthiolate or sodium thiophenolate in DMF yielded the 2‐azabutadiene derivatives (RS)2C=C(H)–N=CPh2 (2) (2a R = iPr; 2b R = Ph). Nucleophilic attack of the sodium salt of ethyl thioglycolate on 1 afforded as the sole product the six‐membered heterocyclic compound ethyl 2‐ethoxycarbonylmethylthio‐5,5‐diphenyl‐5,6‐dihydro‐4H‐1,4‐thiazine‐6‐carboxylate (5). The reaction is initiated by substitution of the two vinyl‐bound chloro substituents to give {EtO(O=)CCH2S}2C=C(H)–N=CPh2 (2c) as intermediate. A mechanism that accounts for the subsequent cyclisation reaction is proposed. The 2‐azabutadiene derivative (PhO)2C=C(H)–N=CPh2 (7) was obtained by the reaction of 1 with sodium phenolate. The regioselectivity of the incoming nucleophile is roughly correlated with its hardness/softness in accord with Pearson’s HSAB principle. The molecular structures of 2a,b, 5 and 7 were determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Dft Calculationscontrasting

confidence: 79%

Section: Discussionmentioning

confidence: 99%

“…Note also that the values of these dihedral angles are 28.7(1)°in 1 (X = Cl) [19] and 38.8(3)°in 2a (X = SiPr). [24] The length of the C(2)-C(3) double bond in 7 …”

Section: Molecular Structures Of 2b Andmentioning

confidence: 99%

“…Part of this work, that concerning the iPrSsubstituted azadiene 2a, has recently appeared in a preliminary communication. [24] Results and Discussion…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation

et al. 2006

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“…Some related structures of alkoxo- (Jacquot et al, 2000), cyano- (Jacquot-Rousseau et al, 2002) and i PrS-substituted (Jacquot-Rousseau et al, 2005) 4,4-dichloro-1,1-diphenyl-2azabuta-1,3-dienes (Jacquot et al, 1999) have been reported. For related literature, see: Tanimoto et al (1976); Truce & Boudakian (1956).…”

Section: Related Literaturementioning

confidence: 99%

4,4-Bis(4-methylphenylsulfanyl)-1,1-diphenyl-2-azabuta-1,3-diene

Kinghat¹,

Boudiba²,

Khatyr³

et al. 2008

Acta Cryst E

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In the title compound, C29H25NS2, both the Cl atoms of the azadiene precursor 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene are replaced by two vicinal S-p-tolyl substituents attached to the terminal C atom of a π-conjugated 2-azabutadiene array. The azadiene chain is planar to within 0.01 Å. One of the phenyl rings seems to be slightly π-conjugated with the azadiene core [dihedral angle 5.1 (2)°].

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(2,2‐Dibromovinyl)ferrocene as a Building Block for the Assembly of Heterodinuclear Complexes – Preparation of an σ‐Alkenylpalladium Complex and Dimetallic Dithioether Complexes

et al. 2007

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The oxidative addition of (2,2‐dibromovinyl)ferrocene [Br2C=C(H)–Fc] (1) to [Pd(PPh3)4] yields the heterodinuclear σ‐alkenyl complex trans‐[{Pd(Br)(PPh3)2}–C(Br)=C(H)–Fc] (2). Nucleophilic attack of sodium thiolates on 1 unexpectedly affords the vinyl thioether derivatives (Z)‐[(RS)(H)C=C(H)–Fc] (4a: R = Ph; 4b: R = tBu; 4c: R = Et). Complexes 4a and 4c can also be prepared by addition of NaSR across the triple bond of Fc–C≡C–H (3). Addition of an excess of NaSR to 1 affords the dithioether derivatives (Z)‐[(RS)(H)C=C(SR)–Fc] (5a: R = Ph; 5b: R = p‐tolyl; 5c: R = Et). An addition/elimination sequence is suggested to account for this surprising result. The yield of 5c is very low due to a competing formation of ethynylferrocene (3). Reaction of 5b with [Re(thf)(CO)3(μ‐Br)]2 and [PtCl2(PhCN)2] leads to the heterodinuclear chelate complexes [Fc{C(S–p‐tolyl)=C(H)(S–p‐tolyl)}Re(Br)(CO)3] (6) and [Fc{C(S–p‐tolyl)=C(H)(S–p‐tolyl)}PtCl2] (7a), respectively. Metathesis of the fluxional compound 7a in the presence of NaI affords [Fc{C(S–p‐tolyl)=C(H)(S–p‐tolyl)}PtI2] (7b). The electrochemical properties of some of these complexes have been studied by means of cyclic voltammetry, and the molecular structures of 1, 2, 3, 4b, 4c and 6 have been determined by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Synthesis and reactivity of an 2-azabutadiene-based π-conjugated dithioether: Formation of a N,S-ligated molybdenum chelate complex and C,N,S-pincer complexes of palladium and platinum

Cited by 15 publications

References 29 publications

Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation

Reactivity of 4,4‐Dichloro‐1,1‐diphenyl‐2‐azabutadiene Towards Alkoxides and Thiolates: Synthesis of Functionalised π‐Conjugated 2‐Azabutadienes and Unexpected 1,4‐Thiazine Formation

4,4-Bis(4-methylphenylsulfanyl)-1,1-diphenyl-2-azabuta-1,3-diene

(2,2‐Dibromovinyl)ferrocene as a Building Block for the Assembly of Heterodinuclear Complexes – Preparation of an σ‐Alkenylpalladium Complex and Dimetallic Dithioether Complexes

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