Synthesis, Structure, and Reactivity of Group 14 Bis(thiophosphinoyl) Metal Complexes

Abstract

Bis(thiophosphinoyl)methane, CH 2 (PPh 2 dS) 2 , and its monolithium salt [Li{(SdPPh 2 ) 2 CH}-(THF)(Et 2 O)] (1) have been used to prepare a series of low-valent group 14 metal complexes. The reaction of lithium salt [Li{(SdPPh 2 ) 2 CH}(THF)(Et 2 O)] (1) with 1 equiv of MCl 2 (M=Ge, Sn) in diethyl ether afforded monomeric organometal(II) chlorides [MCl{CH(PPh 2 dS) 2 }] (M=Ge (2), Sn (3)). Treatment of CH 2 (PPh 2 dS) 2 with equimolar M{N(SiMe 3 ) 2 } 2 (M = Sn, Pb) afforded 1,3dimetallacyclobutanes [M{μ 2 -C(Ph 2 PdS) 2 }] 2 (M = Sn (4), Pb (5)), which are believed to be formed by the dimerization of the metallavinylidene intermediate. Compounds 2 and 5 further reacted with elemental chalcogens (S and Se) to give trans-dithiadigermetane [GeCl{CH(PPh 2 dS) 2 }(μ-S)] 2 (6) and lead(II) chalcogenates [PbE{C(PPh 2 dS) 2 }] (E = S (7), Se (8)), respectively. Compounds 2-8 have been determined by X-ray crystallography.

Octahedral Tin(IV) Complexes of the Chalcogen‐Centered Ligands [EC(PPh2S)2]2– (E = S, Se)

“…Leung and co-workers have shown that the reaction of SnCl 4 with the magnesium reagent MgC(PPh 2 S) 2 (THF) 2 produces the tin(IV) complex Sn[C(PPh 2 S) 2 ] 2 , in which the ligand is bonded in a tridentate (S,C,S) fashion to tin. [10] Interestingly, in this work we isolated small amounts of complex 1b from the reaction of the dilithium reagent Li 2 2 ] (EЈ = S, Se) via chalcogen insertion into Pb-C bonds has been reported previously by Leung et al [11] The 31 P NMR spectra of 1b and 1c in CD 2 Cl 2 show a single resonance at δ = 54.9 and 57.6 ppm, respectively, cf. δ = 61.6 for 1a in CD 2 Cl 2 .…”

“…Although heteroleptic complexes with In III [5] and Te IV , [6] as well as monomeric Pb II derivatives, [11] were previously known, the Sn IV examples 1b and 1c represent the first homoleptic complexes of these interesting ligands with p-block metals or metalloids. However, the low isolated yields and detection of the diselenide [{Li(tmeda)}{SeC(PPh 2 S) 2 2-(EЈ = S, Se) with CuCl 2 .…”

“…0.17 Å for 1a (E = EЈ = Se). The mean Sn-S(P) distances in 1b and 1c are essentially equal [12] The C-S bond www.zaac.wiley-vch.de [11] (TMEDA)InCl[(Se)-C(PPh 2 S) 2 ] [1.938(9) Å], [5] and [{Li(TMEDA)} 2 {SeC(PPh 2 S) 2 }] [1.970(3) Å]. [3] The disparity between the P-S and P-C bond lengths is insignificant when the chalcogen changes from sulfur to selenium in the complexes [Sn{EЈC(PPh 2 S) 2 } 2 ] [2.0261(1) (1b), 2.020(3) (1c) Å and 1.750(4) (1b), 1.745(9) (1c) Å, respectively].…”

The Benzoyl‐Coenzyme A Reductase and 2‐Hydroxyacyl‐Coenzyme A Dehydratase Radical Enzyme Family

“…In the context of the sulfur‐containing systems, the lithium derivative Li 3b was reported more than 40 years ago and used as an in situ reagent to prepare homoleptic transition metal complexes M( 3b ) 2 (M = Fe, Co, Ni) 4. In more recent investigations, Li 3b was employed for the synthesis of heteroleptic C,S ‐coordinated complexes ClM 3b (M = Ge, Sn),5 whereas the metathesis reactions of Li 3b with MCl 3 (M = Al, Ga, In, Bi)6,7 occur with concomitant HCl elimination to give dimeric complexes of methandiide 2b .…”

Synthesis and Redox Behaviour of the Chalcogenocarbonyl Dianions [(E)C(PPh2S)2]2−: Formation and Structures of Chalcogen–Chalcogen Bonded Dimers and a Novel Selone

“…[3] The recent development of a synthesis of the dilithium de-rivative of 2 by Le Floch and co-workers opened the way for wide-ranging investigations of this intriguing dithio PCPbridged ligand. [4,5] A variety of complexes with main group [6] and with early [7] and late transition metals, [4,8] as well as lanthanides [9] and actinides, [10] were subsequently prepared by metathesis of Li 2 2 with metal halides and structurally characterised. The recurring theme in these complexes is the prevalence of strong interactions of the metal with the carbene centre of the ligand 2 (S,C,S-chelation).…”