Karlheinz Guldner

Umsetzungen von schwefeldiimiden mit dreikernigen osmiumclustern: Synthese, kristallstruktur und stereochemie von (μ-H)Os3(CO)8(μ3-AstBu)[μ(N,As)-NSNAstBu2]

Abstract The arsino-substituted sulphur diimide, S(NAs t Bu 2 ) 2 , reacts with Os 3 (CO) 12 in boiling octane to give the trinuclear cluster (μ-H)Os 3 (CO) 8 (μ 3 -As t Bu)[μ( N , As )-NSNAs t Bu 2 ]. An X-ray crystal structure analysis revealed the molecule to contain an open isosceles Os 3 framework capped by a μ 3 -As t Bu ligand. The outer two osmium atoms are fixed by an NSNAs t Bu 2 unit maintaining the sulphur diimide substructure as a μ 2 ( N , As ) bridge. According to temperature-dependent 13 C NMR measurements, the molecule remains rigid in solution up to 70° C.

Cluster build up with arsinidene ligands: synthesis and characterization of some RAs-bridged tri-, tetra- and penta-nuclear osmium carbonyl clusters

Reaction of the labile clusters Os3(CO)11(NCME) (1) with primary arsines (RAsH2; R = Ph, Me, H) yields the arsinidene compounds H2Os2(CO)11(μ3-AsR) (2a: R = Ph; 2b: R = Me; 2c: R = H) in which the cluster framework consists of an HOs(CO)4 and an HOs2(CO)7 unit linked together by a μ3-AsR group. The 1H NMR spectra of 2a2c reveal the presence of two isomers in each case. At elevated temperatures, 2a can be transformed to the AsPh capped cluster (μ-H)2Os3(OC)9-(μ3-AsPh) (3). Treatment of the phenyl derivative 2a with Os sources such as Os3(CO)12, H2Os2(CO)10, or H2OS(CO)4 gives, under thermolytic conditions, the tetranuclear cluster (μ-H)2Os4(CO)12(μ3-AsPh) (4) and the pentanuclear cluster Os5(CO)15(μ4-AsPH) (5).

Triosmium clusters with μ3-AsR group as a building block for hexaosmium-arsenic cluster synthesis. Synthesis and characterisation of [(CO)11Os3As(Os3(CO)9H3)] and [(CO)9H3Os3As(Os3(CO)9H3)]. Crystal structure of [(CO)11Os3As(Os3(CO)9H3)]

Abstract Reaction of the activated cluster [Os 3 (CO) 11 (CNMe)] with primary arsine AsH 3 forms the arsinidine compound [H 2 Os 3 (μ 3 -AsH)(CO) 11 ] ( 1a , 1b ), which on further reaction with [Os 3 (CO) 11 (NCMe)] yields [(CO) 11 Os 3 As(Os 3 (CO) 9 H 3 )] ( 2 ) and with [H 2 Os 3 (CO) 10 ] yields [H 2 Os 3 (CO) 9 As(Os 3 (CO) 9 H 2 )] ( 3 ). Similarly [H 2 Os 3 (CO) 10 ] reacts with AsH 3 at room temperature to afford 3 in good yields. Thermal degradation and rearrangement of 2 gives the pentanuclear cluster [H 2 Os 5 (CO) 17 AsH] ( 4 ).

Bildung eines koordinations-stabilisierten PIIIN3S2-Sechsrings bei der Umsetzung von Pentacarbonylmetall-Komplexen der Organophosphorchloride RPCl2 (R = tBu, Ph, Cl) mit Dikaliumschwefeldiimid, K2SN2. Röntgenstrukturanalyse von (CO)5Cr[P(tBu)NSNSNH]☆

The reaction of the chlorophosphane complexes (CO)5Cr[RPCl2] (R = tBu, Ph) and (CO)5M[PCl3] (M = Cr, W) with the salt K2SN2 (11) in acetonitrile leads to the formation of six-membered PIIIN3S2 rings which are stabilized by coordination to the pentacarbonylmetal fragment. The products (CO)5Cr[P(R)NSNSNH] (R = tBu (1a), Ph (1b)) and (CO)5M[P(NH2)NSNSNH] (M = Cr (4), W (5)) were identified from their mass and IR as well as their 1H, 13C and 31P NMR spectra. In the case of the reaction of (CO)5Cr[tBuPCl2], two products of hydrolysis, (CO)5Cr[tBuP(NH2)2] (2) and SNP(tBu)(NH2)[Cr(CO)5]2 (3) which are formed during chromatographic work-up on silica, were isolated in addition to (CO)5Cr[P(tBu)NSNSNH] (1a). The X-ray diffraction study of 1a revealed an octahedral chromium complex in which the [Cr(CO)5] fragment occupies the axial position at the phosphorus of the six-membered ring ligand. The ring adopts a half-boat conformation, with the N(H) nitrogen out of the plane of the five other ring atoms; it contains a localized sulfur diimide (S=N 1.523(5) and 1.550(7) A, angle NSN 120.1(4)°) and a diaminosulfane (SN 1.690(8) and 1.684(6) A, angle NSN 108.1(4)°) sub-unit. The geometries of the related dithiatriazene six-membered rings are compared with that of 1a.

Synthesis of AsMe2-bridged triosmium clusters: X-ray crystal structures of [Os3H(CO)11(μ-AsMe2)] and [Os3(μ-H)2(CO)8(μ-AsMe2)2]

Abstract Reactions of the activated clusters [Os 3 (CO) 12− n (NCMe) n ] ( n = 1 or 2) with AsHMe 2 give the AsMe 2 -bridged triosmium clusters [Os 3 (μ-H)(CO) 10 (μ-AsMe 2 )] ( 3 ) and [Os 3 (μ-H) 2 (CO) 8 (μ-AsMe 2 ) 2 ] ( 6 ), 3 being formed via the novel intermediate [Os 3 H(CO) 11 (μ-AsMe 2 )] ( 2 ) by cleavage and subsequent formation of an OsOs bond; the X-ray crystal structures of 2 and 6 confirm the presence of μ-AsMe 2 groups.

Application of Reverse Two-Dimensional 1H{15N} NMR Spectroscopy to the Characterization of Two Inorganic Compounds:

Abstract The inorganic ring system linked to the [Cr(CO)5] fragment [R = tBu (1), NH2 (2)], has been studied by reverse two-dimensional, 2D, 1H{15N} NMR spectroscopy. In solution, the exchange of the N-H hydrogen atoms is slow on the NMR time scale. Chemical shifts δ(1H), δ(13C), δ(31P), δ(15N) and coupling constants 1J(31P1H), 2J(31P13C), 1J(31P15N) are reported. In the case of 2, the reduced coupling constants 2K(31PN1H) and 1K(31P15N) have the same sign.

Cyclische Organylarsino-Schwefeldiimide / Cyclic Organylarsino Sulfur Diimides

Abstract The reactions of the bifunctional bis(chloroarsino) compounds MeCH[As(But )Cl]2 and RCH[AsCl2]2 (R = H, Me) with the salt K2SN2 lead to rings and cages containing arsino-substituted sulfur diimide units.

Die Addukte von Bis(di-tert-butylphosphino)- und Bis(di-tertJ-butylarsino)schwefeldiimid mit Cyclopentadienyl-hydridometall- Komplexen CpM(CO)3H (M = Cr, Mo, W) / The Adducts of Bis(di-tert-butylphosphino)- and Bis(di-tert-butylarsino) Sulfur Diimides with Cyclopentadienyl Hydridometal Complexes CpM(CO)3H (M = Cr, Mo, W)

The new sulfur diimides S(NPBut2)2 (a) and S(NAsBut2)2 (b) react with the hydrido- metal complexes CpM(CO)3H (M = Cr (1), Mo (2), and W (3)) to give 1:1 adducts which contain a three-electron acyl-chelate ligand. Only one of the two PBut2 and AsBut2 substituents, respectively, becomes coordinated to the metal; the hydrido ligand of the starting complex (CpM(CO)3H (1-3) is transfered to a N atom of the sulfur diimide system. The structures of the adducts (1a-3a and 1b-3b) are discussed on the basis of their infrared and 1H, 13C, and 31P NMR spectra. The X-ray analysis of 3a confirms the presence of a four-membered metallocycle containing W, C(acyl), N, and P.**