The title complexes (M = Cr (1), Mo (2) and W (3)) are prepared in almost quantitative yield from [t-Bu2PHgN(SiMe3)2] and [M(HPPh2)(CO)5] or in 70% yield by synproportionation of [Hg(t-Bu2P)2] and [Hg{(μ-PPh2)M(CO)5}2]. The compounds are crystalline, air-stable in the solid state but oxygen-sensitive in solution. The solid state structures of 1 and 3 consist of dimers containing four-membered (Hg-P)2 rings with asymmetric phosphido bridges (252.2(2)pm and 268.9(2)pm for 1). The coordination geometry of Hg is almost planar. According to 31P and 199Hg NMR spectroscopy, the solution structure consists of dimers at 173K, whilst dissociation into monomers occurs at ambient temperature.

AbstractHg(II)‐ halogenide bilden mit den sek. Phosphinen (II) die Koordinationsverbindungen (III).

AbstractQuecksilber(II)‐halogenide bilden mit sekundären Phosphanen Koordinationsverbindungen [HgX2(HPR2)n] (1 – 3, X = Cl, Br, I; R = tBu, Cyclohexyl; n = 1,2). Dehydrohalogenierung dieser Komplexe mit Et3N ergibt die unsymmetrischen Phosphinoquecksilberverbindungen XHgPR2 (4,5), die auch aus HgX2 und LiPR2 bzw. durch Synproportionierung von Hg(PR2)2 (R = tBu) und HgX2 zugänglich sind. IHgPCy2 (5c) koordiniert Iodid unter Bildung anionischer Komplexe mit (Hg – P)4‐8‐Ring‐Strukturen 6, 7, in denen erstmals Kopplungskonstanten 2J(199Hg, 199Hg) gemessen werden (2435 – 2959 Hz).

The reaction of HgX2 (X = O3SCF3, 12SO4, OAc) and dicyclohexylphosphine leads to phosphido-bridged ring pentamers [Hg5(μ2-Cy2P)5X5], X = O3SCF3, SO4H or tetramers [Hg4(μ2-Cy2P)4(OAc)4] involving the ten-membered (Hg-P)5 or eight-membered (Hg-P)4 heterocycles. The ring size of these “macrocycles” is under thermodynamic control: The P-Hg-P bonding angles seem to depend on the ligating power of X. The ring structures were characterized by 31P and 199Hg NMR spectroscopy.

The diastereomeric parts of HgP bonded Hg[P(O)(OBun)ph]2 give rise to different 199Hg NMR patterns. No enantiomeric discrimination occurs in the synthesis. Ligand redistribution reactions prevent the separation of the diastereomers.

AbstractDurch Synproportionierung der entsprechenden symmetrischen Hg‐Verbindungen in Pyridin bei Raumtemp. bzw. durch Umsetzung der Hg‐bis‐(triazenate) mit dem Phosphonit werden die Komplexe (I) erhalten, von denen einige als luft‐ und feuchtigkeitsstabile, kristalline Substanzen isoliert werden.

Reaction of HgL2[HL = 1,3-bis(o-fluorophenyl)triazene] with secondary phosphines yields the first monocyclic 6- and 8-membered M–P rings [Hgn(µ2-R2P)nLn](n= 3, R = But or cyclohexyl; (n= 4, R = cyclohexyl or Ph) which are characterized by 1H, 31P, and 199Hg n.m.r. spectroscopy.

The stable title compounds have been prepared by mercuriation of [M(CO)5(PPh2H)] using Hg[N(SiMe3)2]2 and characterized by 31P and 199Hg n.m.r. and mass spectroscopy. The values of 1J(31P–199Hg)(525–725 Hz) are the smallest observed so far for Hg–P bonds.

AbstractDie stabilen Titelverbindungen (III) werden durch Mercurierung von Diphenylphosphin‐pentacarbonyl‐Mo, ‐Woder ‐Cr (I) mit dem Hg(II)‐disilylamid (II) dargestellt und durch "P‐ und ′99Hg‐NMR‐ sowie massenspektroskopische Daten charakterisiert.

At low temperatures (EtO)2P(O)HgY (Y = OAc,O3SCF3,Cl,Br,I,S2CNEt2,S2P(OEt)2, 2,5-pyrrolidinedionato-N, and (EtO)2P(O)) form coordination compounds (EtO)2P(O)c HgY(PR3)n (R = n-Bu, Ph; n = 1–3 depending on Y); 31P and 199Hg NMR data are reported.

AbstractDie Titelverbindungen (I) bzw. (II) wurden durch Reaktion des entsprechenden Phosphinigsäureesters mit HgO in Benzol bzw. mit HgO und den Salzen HgXg in Pyridin dargestellt und durch NMR‐ Daten charakterisiert.

Phosphonito-mercury compounds C6H5(n- C4H9O)PHgX, (X = C6H5(n-C4H9O)P(O), Cl, Br, I, CN, C6H5, OAc, O3SCF3, SCN, SC6H5, SC2H5 and 2,5-pyrrolidindionato-N) were prepared from the corresponding phosphinic acid ester with HgO or with HgO and HgX2. The new compounds are characterized by a HgP bond and decompose easily with fission of this bond. δ(31P), δ(199Hg) and 1J(31P- 199Hg) data are reported.