In reactions with transition metal compounds, tBu2PPP(X)tBu2 (X = Br, Me) acts mainly as a precursor of the tBu2PP ligand, whereas tBu(Me3Si)PPP(Me)tBu2 acts as a precursor of the (Me3Si)PPtBu ligand. Up to now, only Pt(0) d10 ML2 metal centres were found to be able to stabilize the tBu2PP group in ‘pure form’ by means of η2‐coordination (side on). Several compounds of the [{η2 − tBu2PP}Pt(PR3)2] type were sufficiently stable to be isolated and characterized; however, not all of them gave single crystals suitable for X‐ray structure determinations. The X‐ray structures of these compounds and of [{µ − (1,2:2 − η − tBu2PP)Pt(PR3)2} {M(CO)5}] strongly suggest the ethene‐like form of 1,1‐di‐tert‐butyldiphosphene in these complexes. Such a form is also in agreement with RI DFT calculations with SVP basis for free tBu2PP. However, in trapping experiments with cyclic olefins and cyclic dienes tBu2PP exhibits, to some extent, electrophilic ‘singlet carbene’ properties. Copyright © 2002 John Wiley & Sons, Ltd.

Dedicated to Professor Martin Jansen on the occasion of his 60th birthdayThe synthesis, structure, and physical properties of nanosized metal and semiconductor cluster molecules is of topical interest.[1] For the synthesis of metal chalcogenide cluster compounds, we have used the reaction of metal salts MX (M = Cu, Ag, Au; X = Cl, OOCCH 3 ) with bis-or monosilylated main-group element derivates E(SiMe 3 ) 2 or RESiMe 3 (E = S, Se, Te; R = organic group) in the presence of tertiary phosphanes PR 3 .[2] The driving force of this reaction is the formation of XSiMe 3 . In this way, a large number of cluster compounds have been synthesized and structurally characterized, for example, [Cu 146 Se 72 (PPh 3 ) 30 ], [3] [Ag 172 Se 40 -(SenBu) 92 dppp] (dppp = bis(diphenylphosphanyl)propane), [4] [Ag 188 S 94 (PR 3 ) 30 ] (R= nPr, nBu) [5] and [Ag 262 S 100 (StBu) 62 (dppb) 6 ] (dppb = bis(diphenylphosphanyl)butane).[6]Calculations reveal that the PR 3 -stabilized cluster complexes are metastable intermediates on the way to forming the corresponding binary phases. [7] Ternary compounds, however, offer a broader spectrum of tunable properties and are viable candidates for technical use, for example, CuInSe 2 is one of the most promising materials for thin-film technology in solar cells, [8] and conversion efficiencies of up to 18.8 % have been achieved with Cu(In,Ga)Se 2 under laboratory conditions; [9] AgInS 2 , AgIn 5 S 8, and AgGaS 2 are of interest as materials for non-linear optical devices.[10] This prompted us to investigate the synthesis of ternary cluster compounds composed of elements of Group 11, 13, and 16. Similar to the synthetic approach for binary clusters outlined above, the reaction of mixtures of the metal halides with E(SiMe 3 ) 2 (E = Se, S) yielded cluster compounds such as [Cu 11 In 15 Se 16 -(SePh) 24 (PPh 3 ) 4 ], [11]

International audienc

No abstract

CuX (X = Cl, CH3COO) bzw. AgOC(O)C6H5 und GaCl3 reagieren in THF mit S(SiMe3)2 bzw. Se(SiMe3)2 in Anwesenheit von PPh3 zu [Cu6Ga8Cl4S13(PPh3)6] (1), [Cu6Ga8Cl4Se13(PPh3)6] (2), [Ag6Ga8Cl4S13(PPh3)6] (4) und [Ag6Ga8Cl4Se13(PPh3)6] (5). Verwendet man anstelle von PPh3 das Phosphan PnPr2Ph, so läßt sich nach Überschichten mit n‐Hexan die Verbindung [Cu6Ga8Cl4Se13(PnPr2Ph)12] (3a, 3b) kristallisieren. Durch Umsetzung von CuCl, GaCl3 und PnPr3 mit Se(SiMe3)2 in THF erhält man den ionischen Cluster (HPnPr3)2[Cu2Ga4Cl4Se6(PnPr3)4] (6). Die Strukturen der Verbindungen 1—6 konnten durch Einkristall‐Röntgenstrukturanalyse aufgeklärt werden. TGA‐MS‐Messungen und Pulverdiffraktogramme der Rückstände zeigen die potentielle Verwendbarkeit der Cluster als Prekursormaterialien zur Darstellung der entsprechenden ternären Festkörperverbindungen.