J.D. Woollins

Nitro–ruthenium(II)–arylazoimidazoles: synthesis, spectra, crystal structure and electrochemistry of dinitro-bis{1-alkyl-2-(arylazo)imidazole}ruthenium(II). Nitro–nitroso derivatives and reactivity of the electrophilic {Ru-NO}6 system

Silver ion assisted aquation of blue cis,trans,cis-RuCl2(RaaiR′)2 (4–6) leads to solvento species, blue–violet cis,trans,cis-[Ru(OH2)2(RaaiR′)2](ClO4)2 [RaaiR′ = p-R–C6H4–NN–C3H2–NN-1-R′ (1–3), abbreviated as N,N′-chelator where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1/4/7/10), CH2CH3(2/5/8/11), CH2Ph (3/6/9/12)] that have been reacted with NO2− in warm ethanol resulting violet dinitro complexes of the type, Ru(NO2)2(RaaiR′)2 (7–9). The structure in one case, [Ru(NO2)2(HaaiCH2Ph)2] (9a), has been established by X-ray diffraction as the cis-Ru(NO2)2 motif along with trans-N,N and cis-N′,N′ dispositions of the chelator N atoms around the coordination sphere. The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the compounds 7b–9b with conc. HClO4 nitro–nitrosyl derivatives, [Ru(NO2)(NO)(MeaaiR′)2](ClO4)2 (10b–12b), are isolated. The solution structure and stereoretentive transformation in each reaction step have been established by 1H NMR results. All the complexes exhibit strong MLCT transitions in the visible region. They are redox active and display one metal-centred oxidation and successive ligand-based reductions. The redox potentials of Ru(III)/Ru(II) (E1/2M) of 10b–12b are anodically shifted by ∼0.2 V as compared to those of dinitro precursors 7b–9b. The ν(NO) > 1900 cm−1 strongly suggests the presence of linear Ru–N–O bonding. The electrophilic behaviour of metal bound nitrosyl has been proved in one case (12b) by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group, and the heteroleptic tris-chelates thus formed are characterised.

The synthesis and characterisation of bis(diisopropylphosphoryl)ferrocene Fe[(η5-C5H4)P(O)iPr2]2, bis(diisopropylthiophosphoryl)ferrocene Fe[(η5-C5H4)P(S)iPr2]2, and bis(diisopropylselenophosphoryl)ferrocene Fe[(η5-C5H4)P(Se)iPr2]2, the oxidised derivatives of bis(diisopropylphosphino)ferrocene

Abstract The synthesis and spectroscopic characterisation of three chalcogenophosphoryl ligands derived from ferrocene is reported. The synthesis was based on the oxidation of Fe[(η5-C5H4)PiPr2]2 by elementary sulfur and selenium, and hydrogen peroxide, respectively. All new compounds were characterised by X-ray crystallography and comparison with their aryl analogues was made. Contrary to Fe[(η5-C5H4)P(E)Ph2]2 (E=O, S, Se), the prepared compounds are not centrosymmetric, with the iso-propyl groups showing more flexibility than the phenyl substituents.

Carbonyl complexes of ruthenium(II) with unsymmetrical phosphine–phosphinesulfide ligands of the type Ph2P(CH2)nP(S)Ph2, n=1–4

Reaction of [Ru(CO) 2Cl 2] n with ligands Ph 2P(CH 2)nP(S)Ph 2 (n0/1(a), 2(b), 3(c), 4(d)) in 1:1 molar ratio produces complex cis[Ru(CO) 2Cl 2(PS/S)](1a)(PS/S0/h 2-(P, S) coordinated) and cis-[Ru(CO)2Cl2(P/S)](1b/d)(P/S0/h 1-(P) coordinated), while 1:2 molar ratio yields complex of the type cis-[Ru(CO) 2Cl 2(P/S) 2](2a/d). The complex 2a undergoes partial decarbonylation reaction inCH 2Cl 2/hexanesolutiontogiveanewchelatedcomplex[Ru(CO)Cl(PS/S) 2]Cl(2a?).AbstractionofhalidewithAgClO 4fromthe non-chelated complexes 1b/d and 2a/d afford corresponding chelated complexes [Ru(CO) 2Cl(PS/S)](ClO 4)(3b/d) and [Ru(CO) 2(PS/S) 2](ClO 4)2(4a/d). The molecular structure of the complex 2a? has been determined by single crystal X-ray diffraction. The ruthenium atom is at the centre of slightly distorted octahedral structure having the two phosphorus atoms of the twochelatedP,Scoordinatedligandsattrans toeachother,oneCOgroupandClatomcompletingthecoordinationsphere.Other complexes have been characterized by elemental analysis, IR, 1H and 31P {H} NMR spectroscopy.

Copper(II) oxalate and oxamate complexes

Reaction of CuII salts with phenanthroline and oxalate (ox) or oxamate (oxm) gives [Cu(phen)(ox)(H2O)] · H2O or [Cu(phen)(oxm)(H2O)] · H2O complexes while direct treatment of CuII salts with oxalate or oxamate gives [NH4]2[Cu(ox)2] and [Cu(oxm)2(H2O)2] respectively. The X-ray structures of one example of each system, aquo-oxamato-phenanthroline-copper(II)-dihydrate and the polymeric ammonium-bis(aquo)-tetraoxalato-dicopper(II)-dihydrate, are reported.

8-Bromo-naphthalen-1-amine.

The title compound, C10H8BrN, was obtained by slow addition of sodium azide to 8-bromo-1-naphthoic acid, followed by addition of aqueous ammonia. The crude product was crystallized from petroleum ether to give pink crystals. Compared to other 1,8-disubstituted naphthalene compounds, this compound exhibits less strain between the 1 and 8 substituents. Additionally, the NH protons form both intra- and intermolecular hydrogen bonds. The naphthalene units are arranged in a herring-bone stacking motif.

5-Benzyl-idene-2,3-diphenyl-1,2-selenaphosphole-2-selenide.

The title compound, C(23)H(19)PSe(2), has a central five-membered twist C(3)PSe ring conformation. One phenyl ring substituent, attached to an sp(2) carbon, is approximately coplanar with the C(3)PSe ring whilst the other organic substituents, attached to an sp(3)-carbon and a P(V) atom, lie on the same side of the ring.

1,5,6-Triphenyl-8-oxa-7-selena-6-phos­phabicyclo­[3.2.1]octane-6-selone

The structure of the title compound, C23H21OPSe2, consists of fused puckered five- and six-membered rings, PSeC2O and C5O, respectively, with a C2O bridgehead. The C5O ring adopts a chair conformation, whilst the C2PSeO ring has an envelope conformation.

Reaction of Naphthalenedithiadiphosphetanedisulphide with Ethylene Glycol

Reaction of the title compounds (molar ratio 1:30) in refluxing toluene results in cleavage of one of the P-S-P bridges in naphthalenedithiadiphosphetanedisulphide 1 and formation of a new heterocycle 2 which contains a C3P2S ring with the phosphorus atoms substituted by OCH2CH2OH groups; reaction at 140°C results in complete desulphuration of napthalenedithiadiphosphetanedisulphide 1 and formation of the new heterocycle 1,8-naphthodiphosphonic acid anhydride 3 which contains a C3P2O ring. 2 and 3 were characterised by microanalysis, IR, 31P NMR and X-ray crystallography: 2, monoclinic, space group C2/c with a = 17.564 (4), b = 12.475 (2) and C = 16.423 (3) A, β = 102.98 (3·), calculated density 1.54 g/cm3, Z = 8, reflections collected 1089, final R value 0.0501; 3, monoclinic, space group P21/c with a = 7.961 (2), b = 8.275 (2) and c = 16.192 (5) A, β = 96.93 (3), calculated density 1.694 g/cm3, Z = 4, reflections collected 1837, final R value 0.044. No reaction occurred when 3 was heated with H2O.

Novel Fluorinated Phosphorus–Sulfur Heteroatom Compounds: Synthesis and Characterization of Ferrocenyl- and Aryl-Phosphonofluorodithioic Salts, Adducts, and Esters

A series of novel ferrocenyl- and aryl-phosphonofluorodithioic salts, adducts, and esters has been prepared. The reaction of 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide {[FcP(μ-S)S]2, FcLR} with dry KF or tetrabutylammonium fluoride (TBAF) led to the corresponding potassium and tetrabutylammonium salts of ferrocenyldithiofluorophosphinic acids. Treating potassium ferrocenyldithiofluorophosphinic acid with an equimolar amount of tetraphenylphosphonium chloride readily yielded the corresponding organic adducts, and with mono- and di-halogenated alkanes generated a series of the corresponding esters of ferrocenylphosphonofluoridodithioates. Similarly, using 1,3-epithionaphtho[1,8-cd][1,2,6]oxadiphosphinine 1,3-disulfide or Belleau’s Reagent in place of FcLR resulted in the corresponding novel salts, adducts, and ester derivatives. All new compounds have been characterized by means of multi-NMR (1H, 13C, 31P, 19F) spectroscopy and accurate mass measurement in conjunction with single crystal X-ray crystallography of four structures.

(Disulfur dinitrido)triphenyl­anti­mony(V)

The title compound, [Sb(C6H5)3(N2S2)], contains a molecular entity that is very similar to that of the known polymorph of Sb(S2N2)Ph3 [Kunkel et al. (1997 ▶). Z. Naturforsch. Teil B, 52, 193–198], differing only in the orientation of the phenyl rings. The bond order in the SNSN unit is S—N=S=N, consisting of one long S—N bond, an intermediate length N=S bond and a short S=N bond.