Komplexe mit Kohlenstoffsulfiden und ‐seleniden als Liganden, XVIII. Umwandlung η²‐gebundener Heteroallene (CS₂, CSSe und CSe₂) in CS‐, CSSe und C₂Se‐Chelatliganden

Abstract

PPh3)2Pt(q2-CS2) (1) reagiert rnit PMe3, PMe2Ph und PMePh2 zu den (Trithiocarbonato-S,S')platin(II)-Komplexen (PR3)2Pt(q2-S2CS) (2-4). Analog entsteht bei der Umsetzung von (PPh,),Pt(q2-CSSe) mit PMe3 die Verbindung (PMe3)2Pt(q2-Se2CS) (6). Die Reaktion von (PPh,)2Pt(q2-CSe2)d(7) rnit PMe2Ph fiihrt zu dem Metallaheterocyclus (PMe2Ph)-(PPh3)PtSeC(Se)Se (Se) (8). Bei der Einwirkung von C 0 2 auf (PPhs)2Pt(C2H4) bildet sich der Carbonatoplatin(T1)-Komplex (PPh3)2Pt(q2-02CO) (9). Ein Vorschlag zum Bildungsmechanismus der erhaltenen Produkte wird diskutiert. Metal Complexes with Carbon Sulfides and Selenides as Ligands, XVIII') Conversion of q'-Bonded Heteroallenes (CS, C S , and CSeJ into the Chelate LigandsCg-, CSSei-, and C2Sei-(PPh3kPt(q2-C&) (1) reacts with PMe3, PMe,Ph, and PMePh2 to produce the (trithiocarbonato-S,S')platinum(II) complexes (PR3),Pt(q2-S2CS) (2 -4). Similarly, on treatment of (PPh,kPt(q2-CSSe) with PMe, the compound (PMe&Pt(q2-Se2CS) (6) is formed. The re-(7) with PMe2Ph leads to the metallaheterocycle (PMe2Ph)carbonatoplatinum(I1) complex (PPh3)2Pt(qz-OzCO) (9) is obtained from (PPh,)2Pt(C2H4) and COz. The mechanism of formation of the chelate compounds is discussed.

Palladium(II) and Platinum(II) Complexes with Bisphosphanes, [S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Chelating Ligands

“…From the satellites in the spectra of the platinum complexes 4a–4c and 8 , substantially large 195 Pt– 31 P coupling constants of 3000–3170 Hz could be determined. The UV spectra of 3a–3d, 4a–4c, 7 and 8 show a maximum at 340–350 nm, which is at a similar position as found for the palladium and platinum trithionates [(L–L) M (S 2 CS)] (L–L = dppe, dcpe, dmpe) 8,9…”

Complexes with S-Donor Ligands. 6. Synthesis of the First Family of (Trithiocarbonato)gold Complexes. Crystal Structure of [(PPh3)2N][AuCl2(CS3)]

“…We report here a gold(I) complex showing an μ 2 -η 2 -trithiocarbonato ligand (see F in Chart ) and the first crystal structure of a (trithiocarbonato)gold(III) complex. These and the other CS 3 complexes (Ti, V, Cr, 5a, Mo, Mn, Re,5c Fe, Co, 5a,b,, Rh, Ni, 5a,b,,19a, Pd, 21c,d, Pt, 21c,d,22d, Cu, ,, Ag, Zn, Cd, , Tl, Sn, As, Sb, Bi, and U , have been prepared by reacting (i) CS 2 with oxo, sulfide, ,7a, dithiocarbonate, carbonyl, , or carbonylate complexes;5c (ii) trithiocarbonato complexes or salts with aquo, 5a,19a, acetato, perchlorato,22a halo, ,21a,d acetylacetonato, 9b,c, sulfide, , or thf complexes; 5a,,19a (iii) sulfur with CS 2 5b,c,14 or with NaOEt and R 3 PCS 2 complexes;19b (iv) PPh 3 with perthiocarbonato 21b,26 or CS 2 33 complexes; or (v) by decomposition of a xanthato complex 11c. We report here the synthesis of the first (trithiocarbonato)gold(I) complex by reacting [Au(SH) 2 ] - with CS 2 .…”

Synthesis and Characterisation of the First Cyanodiselenoimidocarbonate [C2N2Se2]2− Complexes

“…Other well-established selenium donor ligands include the selenoethers [15Ϫ18] and the pseudohalide selenocyanate. [19,20] However, there are very few Se,Se-bidentate ligands reported in the literature, which include a series of (diselenothiocarbonato)bis(phosphane)platinum compounds, [21] two triselenocarbonate complexes [(η-5 C 5 H 5 )Co(CSe 3 )(PMe 3 )] [22] and [Ba(CSe 3 )], [23] a (2,4-dioxo-3,3-pentanediselenolato)bis(phosphane)platinum complex, [24] two diselenocarbonimidato compounds, [25,26] [ [27] and a series of [Pt{Se 2 P(Se)(C 6 H 5 )}(PR 3 ) 2 ] complexes. [28] As part of our program studying the properties of chalcogen donor systems we have recently reported a series of cyanodithioimidocarbonate complexes.…”