Cl i /Br-Substitution in der Wolframchlorosäure (H3O)2[W6Cl 8 i ]Cl 6 a ·6H2O

A method for preparing chlorotungstic acid $$(H_3 O)_2 [W_6 Cl_8 i]Cl_6 a \cdot 6H_2 O$$ in good yield is given. On thermal degradation of the acid, the stages $$(H_2 O)_2 [W_6 Cl_8 ]Cl_6 ,[W_6 Cl_8 ]Cl_4 \cdot 2H_2 O and [W_6 Cl_8 ]Cl_4 $$ are isolable. Chlorotungstic acid and its partial Br ⁱ -substitution products can be precipitated almost quantitatively as $$(Oxin \cdot H)_2 [W_6 X_8 ]X_6 $$ When boiled with strong aqueous or aqueous-ethanolic HBr the substitution of Cl ^a and also partial Cl ⁱ /Br substitution occurs. In the same way I ⁱ can be introduced. The inverse reaction (substitution of Br ⁱ by Cl) is not possible. In ethanolic HB in the case of Cl ⁱ /Br substitution an induction period is observed.     

Reactivity of the hydrido/nitrosyl radical MHCl(NO)(CO)(P(i)Pr(3))(2), M = Ru, Os

The reaction of equimolar NO with the 16 electron molecule RuHCl(CO)L(2) (L = P(i)Pr(3)) proceeds, via a radical adduct RuHCl(CO)(NO) L(2), onward to form RuCl(NO)(CO)L(2) (X-ray structure determination) and RuHCl(HNO)(CO)L(2), in a 1:1 mole ratio. The HNO ligand, bound by N and trans to hydride, is rapidly degraded by excess NO. The osmium complex behaves analogously, but the adduct has a higher formation constant, permitting determination of its IR spectrum; both MHCl(CO)(NO)L(2) radicals are characterized by EPR spectroscopy, and DFT calculations on the Ru system show it to have a "half-bent" Ru-N-O unit with the spin density mainly on nitrogen. DFT (PBE) energies rule out certain possible mechanistic steps for forming the two products. A survey of the literature leads to the hypothesis that NO should generally be considered as a (neutral) Lewis base (2-electron donor) when it binds to a 16 electron complex which is resistant to oxidation or reduction, and that the resulting N-centered radical has a M-N-O angle of approximately 140 degrees, which distinguishes it from NO(-) (bent at <140 degrees ) and from NO(+) (>170 degrees ).     

Di- and tri-nuclear osmium carbonyl chloride complexes: x-ray structures of Os2(CO)8Cl2 and Os3(CO)12Cl2

Summary Os₂(CO)₈Cl₂ (1) is orthorhombic P2₁2₁2₁ witha=9.3599(9),b=9.879(2),c=16.014(3), V=1480³, D_c=3.03 Mgm^–3 for Z=4. Structure solved by Patterson methods. Final R=0.038, R_w=0.038 [w=(²F)] for 1270 observed reflections and 141 parameters. Os₃(CO)₁₂Cl₂ (2) is monoclinic C2/m witha=12.105(3), b=10.612(3),c=8.798(1) , =117.02(2)°, V=1006³, D_c=3.22 Mgm^–3 for Z=2. Structure solved by Patterson methods. Final R=0.036, R_w=0.037 (w=(²F)^–) for 821 observed reflections and 75 parameters.Complex(1) has an osmium-osmium single bond 2.897(1), with the chloride ligands in equatorial positions,(2) has a linear triosmium chain with osmium-osmium single bonds 2.893(1) and the chloride ligands occupy equatorial sites on the terminal osmium atoms. Both(1) and(2) are isostructural with their osmium carbonyl iodide analogues.     

Bildung und NMR-spektroskopische Charakterisierung von Alk-(ar-)oxyderivaten von Trichlorphosphazen-N-phosphoryldichlorid,Cl3PN?P(O)Cl2, Imido- und N-Methylimidodiphosphoryltetrachlord,Cl2P(O)NHP(O)Cl2 bzw. Cl2P(O)N(CH3)P(O)Cl2

Formation and N.M.R.-Spectroscopic Characterization of Alk-(ar-)oxy Derivatives of Trichlorophosphazene-N-phosphoryldichloride, Cl₃P?N? P(O)Cl₂, Imido- and N-Methylimidodiphosphoryltetrachloride, Cl₂P(O)NHP(O)Cl₂ and Cl₂P(O)N(CH₃)P(O)Cl₂ The ester chlorides and esters P₂NOCl_5?x(OR)_x (x = 1?5), P₂(NH)O₂Cl_4?x(OR)_x (x = 1–4) and P₂(NCH₃)O₂Cl_4–x(OR)_x (x = 1–4) derived from the title compounds by substitution of chlorine atoms by alk- or aroxy groups are characterized by their ³¹P-n.m.r. data. The possibilities for forming these compounds by alcoholysis, chloridolysis, dealkylation and P? N-bond formation are discussed.     

Multiple mixed-valence behavior in trans,trans-[(tpy)(Cl)2Os(III)(mu-1,3-N3)Os(III)(Cl)2(tpy)]+. An azido bridge from the reaction between trans-[Os(VI)(tpy)(Cl)2(N)]+ and NH3

Reaction between the Os(VI)-nitrido complex, trans-[OsVI(tpy)(Cl)2(N)]PF6 (tpy = 2,2':6',2' '-terpyridine), and ammonia (NH3) under N2 in dry CH3CN gives the mu-1,3-azido bridged [OsII-N3-OsII]- dimer, trans,trans-NH4[(tpy)(Cl)2OsII(N3)OsII(Cl)2(tpy)]. It undergoes air oxidation to give the [OsIII-N3-OsIII]+ analogue, trans,trans-[(tpy)(Cl)2OsIII(N3)OsIII(Cl)2(tpy)]PF6 ([OsIII-N3-OsIII]PF6), which has been isolated and characterized. The structural formulation as a mu-1,3-N3 bridged complex has been established by infrared and 15N NMR measurements on the 15N-labeled forms, [OsIII-14N=15N=14N-OsIII]+, [OsIII-15N=14N=15N-OsIII]+, and [OsIII-15N=15N=15N-OsIII]+. Cyclic voltammetric measurements in 0.2 M Bu4NPF6/CH3CN reveal the existence of five chemically reversible waves from 1.40 to -0.12 V for couples ranging from OsV-OsIV/OsIV-OsIV to OsIII-OsII/OsII-OsII. DeltaE1/2 values for couples adjacent to the three mixed-valence forms are 0.19 V for OsIII-OsII, 0.52 V for OsIV-OsIII, and >0.71 V for OsV-OsIV. In CH3CN at 60 degrees C, [OsIII-N3-OsIII]+ undergoes a [2 + 3] cycloaddition with CH3CN at the mu-N3- bridge followed by a solvolysis to give trans-[OsIII(tpy)(Cl)2(5-MeCN4)] and trans-[OsIII(tpy)(Cl)2(NCCH3)]PF6.     

TcCl4(H2O)2] and [Cl3(H2O)2TcOTc(H2O)2Cl3]--two molecular intermediates of the hydrolysis of technetium(IV)

Two molecular intermediates of the hydrolysis of technetium tetrachloride, cis-[TcCl4(H2O)2] and [Cl3(H2O)2TcOTc(H2O)2Cl3], were isolated and structurally characterised, suggesting that the hydrolytic degradation of technetium(IV) compounds occurs stepwise with the polymeric 'TcO2...nH2O' as a less defined final product.     

On the Reactivity of P Trichloro N Dichlorophosphor-Yl-Mdnophosphazene Cl3P=N-P(O)Cl2

Abstract

In this poster we give the results of some reactions of P trichloro N dichlorophosphoryl monophosphazene Cl₃P=N-P(O)Cl₂ (I) with inorganic and organic nucleophilic reagents.     

Die darstellung von [(CH3)3PRu(CO)2Cl2]2 und [(Ch3)3P]2Ru(CO)2Cl2; Eine berichtigung zu: Die alkoholyse des triethylsilans katalysiert von [(Ch3)3P]2Ru(CO)2Cl2

The ruthenium(II) complex used as a catalyst in reactions of alcohols and Et₃SiH proved to be the dimer [(CH₃)₃PRu(CO)₂Cl₂]₂ and not the complex [(CH₃)₃P]₂ Ru(CO)₂Cl₂. Both complexes were prepared, characterized and their catalytic properties were compared.     

ClONO2与Cl(2P3/2)的反应机理

在密度泛函理论B3LYP/6-31G^*水平上,研究了ClONO₂+Cl(²P_3/2)Cl₂+NO₃和ClONO₂+Cl(²P_3/2)ClO+ClONO(cis)及ClONO₂+Cl(²P_3/2)ClOCl+NO₂的反应机理.计算得到各可能反应途径的过渡态,并经过内禀反应坐标(IRC)分析加以证实.反应ClONO₂+Cl(²P_3/2)Cl₂+NO₃反应活化能垒最低,为4.5kJ/mol,是反应主通道.     

Reaction of Os3H2(CO)9(C6H4) with diphenylacetylene: the formation and structural characterisation of Os3(CO)7(C6H4)[PhCC(H)Ph]2

The reaction of the 'benzyne' cluster Os₃H₂(CO)₉(C₆H₄) with diphenylacetylene affords the new compound Os₃(CO)₇(C₆H₄)[PhCC(H)Ph]₂; a single crystal X-ray analysis of this product shows that two PhCC(H)Ph units and the benzyne moiety are bonded to the Os₃ core as separate ligands, and that under these conditions there is no ligand condensation.