Insertion of phenylethyne-thiolate or -selenolate into metal–carbene bonds: synthons for co-ordinated thioacyl or selenoacyl anions and for anionic thiocarbene or selenocarbene complexest

Abstract

Reaction of lithium ethynethiolate or ethyneselenolate, LiX'CrCPh (Xl = S or Se), with carbene complexes [M(CO),{C(OR1)Ph}] (M = Cr or W; R1 = M e or Et) afforded, by the formation of carbon-carbon bonds, a series of adducts, Li[M (CO),{C(OR') PhC( Ph)=C=X'}]. The adducts reacted regioselectively with electrophiles: acidification with HCI gave a,p-unsaturated thio-and seleno-aldehyde complexes, [M(CO),{X'=CHC(Ph)=C(OR') Ph}], alkylating agents [Et,O] [BF,] or Me1 gave a,P-unsaturated thio-or seleno-carbene complexes, [M (CO),{C(X1R3) -C( Ph)=C(OR') Ph] (X1R3=SEt, SMe, or SeEt), which cleanly and spontaneously converted into sulphur-or selenium-co-ordinated indene derivatives, [M(CO),{(X1R3)CH(C,H,-0)-C(OR1)=CPh}] (X'R3=SEt or SeEt), and, finally, disulphides R4SSR4( R4=Me, Et, or Ph) or the diselenide PhSeSePh yielded thio-or seleno-ester complexes[ M (CO),{X1 =C(XZR4)C( Ph)= C( OR') Ph] (XZR4=SMe, SEt, SPh, or SePh). Four X-ray crystal-structure determinations established the stereochemical configurations of selected members of the various classes of acyclic products.The isomeric compound to one of the thioaldehyde complexes, [W( CO),{S=C( Ph)CH=C(OEt) Ph}], obtained from the adducts with X = S or Se and R' = Et on acidification in the presence of CS, or CSe,, was also characterized structurally by single-crystal X-ray diffraction.

Synthesis of Alkynechalcogenolato Complexes of Titanocene(IV) and Samarocene(III) and Formation of a Ti2Ni Trinuclear Cluster [Cp2Ti(μ-SC⋮CPh)2]2Ni

“…Weigand and Raubenheimer prepared LiEC⋮CR (E = S, Se; R = Ph, SiMe 3 , etc.) using the method analogous to eq 1 for the reactions with CpRuClL 2 (L = PPh 3 , PMe 3 ), L 2 PtCl 2 (L = PPh 3 , 1 / 2 dppe), and carbene complexes of chromium and tungsten. , However the lithium alkynechalcogenolates obtained from one-pot reactions of equimolar amounts of alkyne, n BuLi, and 1 / 8 S 8 or Se was used for the subsequent reactions without isolation of LiEC⋮CR. Therefore, we reexamined preparation of lithium alkynechalcogenolates, to find that LiSC⋮C t Bu and LiSeC⋮CPh were readily obtained as white solids from the reactions of the corresponding lithium alkynides with S 8 and gray selenium, respectively.…”

“…While alkali metal salts of alkynechalcogenolate have been known for some time, there are only a few examples of their transition metal complexes. Alkynethiolate complexes, CpRu(SC⋮CR)L 2 and L 2 Pt(SC⋮CR) 2 were prepared from reactions of LiSC⋮CR (R = Ph, SiMe 3 , (C 5 H 5 )Fe(C 5 H 4 )) with CpRuClL 2 (L = PPh 3 , PMe 3 ) and L 2 PtCl 2 (L = PPh 3 , 1 / 2 dppe), respectively, while the Fisher-type carbene complexes M(CO) 5 {CPh(OEt)} (M = Cr, W) were found to react with LiEC⋮CPh and gaseous HCl to give M(CO) 5 {ECHC(Ph)C(OEt)Ph} (E = S, Se). , Interestingly the treatment of [(μ-S 2 )Fe 2 (CO) 6 ] with LiC⋮CR and subsequent addition of alkyl halide or acyl halide gave rise to alkynethiolate complexes, [(μ-SC⋮CR)(μ-SR‘)Fe 2 (CO) 6 ] (R = Ph, n -C 4 H 9 , n -C 5 H 11 , SiMe 3 ; R‘ = Me, Et, PhCH 2 , CH 2 C(O)CH 3 , CH 3 C(O), (CH 3 ) 3 CC(O)) . However, crystal structures of these alkynechalcogenolate complexes have not been determined.…”

Dehydration Reaction of Hydroxyl Substituted Alkenes and Alkynes on the Ru2S2 Complex

“…The structure of complex 11 is shown in Figure . The SC bond distance of 1.631(10) Å in 11 is slightly shorter than those of the η 1 -SC complexes, such as E -[W(CO) 5 {SCHC(Ph)C(OEt)Ph} (1.63(2) Å), E -[W(CO) 5 {SC(Ph)CHC(OEt)Ph} (1.667(6) Å), E -[W(CO) 5 {SC(SEt)C(Ph)C(OEt)Ph} (1.657(8) Å), and [CpRu{( S , S )-CHIRAPHOS}(SC 19 H 14 O)] + (1.655(8) Å) . The sum of the angles around C2 in 11 is approximately 360°, and the carbon atom is sp 2 hybridized.…”

Organometallic Selenolates. 5.1 Synthesis and Complexing Properties of 2-Propene- and 2-Methyl-2-propeneselenolato Molybdenum and Tungsten Compounds. Crystal Structures of cp(CO)3WSeCH2C(CH3)CH2, [cp(CO)2MoSeCH2C(CH3)CH2]2, [cp(CO)3Mo(μ-SeCH2C(CH3)CH2)W(CO)5], [cp(CO)3Mo(μ-SeCH2C(CH3)CH2)Mo(CO)5<

“…This electronic effect also influences the M(0)−Se bonds in these complexes, leading to bond lengths of nearly the same value [ 6 , W−Se 2.6881(1) Å; 7 , Mo−Se 2.7014(7) Å; 8 , Mo−Se 2.6762(9) Å]. Several structures of W(CO) 5 -substituted organoseleno compounds have been determined and the W(0)−Se bond lengths are in the range 2.619(3)−2.696(1) Å, whereas crystal structures of the Mo(CO) 5 -substituted derivatives are not known. In the cyclic bis(selenolato) complex 3 , the corresponding Mo(II)−Se bond lengths are shorter (average 2.6327(8) Å), because the formal positive charges on the selenium can be delocalized into the Mo 2 Se 2 ring, reducing the electronic repulsion between the Mo and Se atoms.…”