Study on the reactions of the dinitrogen complexestrans-[M(N2)2(Ph 2PCH2CH2PPh 2)2] (M=Mo or W) with ethyldiazoacetate: Formation of an Azo compound and of a phosphazene species

Complextrans-[Mo(N₂)₂(dppe)₂] (dppe=Ph ₂PCH₂CH₂PPh ₂) reacts with NN=CHCOOEt in benzene solution to afford benzene-azomethane,Ph-N=N-CH₃, as the main organic product. However, the phosphazene speciesPh ₂P(N₂CHCOOEt)(CH₂CH₂)P(N₂CHCOOEt)Ph ₂ is formed by irradiating aTHF solution oftrans-[W(N₂)₂(dppe)₂] in the presence of ethyldiazoacetate; in moist solution, the phosphazene bonds undergo a partial hydrolysis, and the phosphonium species [Ph ₂P(NHNCHCOOEt)(CH₂CH₂)P(NHNCHCOOEt)Ph ₂]²⁺ appears to be formed.

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Untersuchungen zu den Reaktionen der Distickstoff-Komplexetrans-[M(N₂)₂(Ph ₂PCH₂CH₂PPh ₂)₂] (M=Mo oder W) mit Ethyldiazoacetat: Die Bildung einer Azoverbindung und eines Phosphazens

Zusammenfassung Die Komplexetrans-[Mo(N₂)₂(dppe)₂] (dppe=Ph ₂PCH₂CH₂PPh ₂) reagieren mit NN=CHCOOEt in benzolischer Lösung zuPh-N=N-CH₃ als organischem Hauptprodukt. Andererseits wird bei der Bestrahlung vontrans-[W(N₂)₂(dppe)₂] inTHF-Lösung in der Gegenwart von Ethyldiazoacetat das PhosphazenPh ₂P(N₂CHCOOEt)(CH₂CH₂)P(N₂CHCOOEt)Ph ₂ gebildet; in feuchter Lösung erleidet die Phosphazen-Bindung eine teilweise Hydrolyse und die Phosphonium-Spezies [Ph ₂P(NHNCHCOOEt)(CH₂CH₂)P(NHNCHCOOEt)Ph ₂]²⁺ scheint gebildet zu werden.

     

Preparation and Properties of Molybdenum and Tungsten Dinitrogen Complexes. 30.1 Syntheses of Zero-Valent Molybdenum Complexes with the DMF Ligand: The Crystal Structure of Trans-[Mo(CO)(DMF)(Ph2PCH2CH2PPh2)2]

Abstract

Treatment of trans-[Mo(N₂)₂(dpe)(dpm)] (dpe = Ph₂PCH₂CH₂PPh₂, dpm = Ph₂PCH₂PPh₂) or trans-[Mo(N₂)₂(dpe)(dpp)] (dpp = Ph₂PCH₂CH₂CH₂PPh₂) with excess DMF in benzene at reflux under Ar resulted in the formation of trans-[Mo(CO)(DMF)(dpe)(dpm)] or trans-[Mo(CO)(DMF)(dpe)(dpp)]. X-ray structural analysis of trans-[Mo(CO)(DMF)(dpe)₂] was performed using single crystals isolated as the minor product from the reaction mixture of trans-[Mo(N₂)₂(dpe)(dpp)] and DMF. Crystal data: C₅₆H₅₅O₂NP₄Mo, monoclinic, space group P2₁, a = 11.145(4), b = 23.425(5), c = 10.516(3) Å, β = 117.17(2)° V = 2442.6(13) ų, D _calcd = 1.35 g/cm³ for Z = 2. This disclosed the relatively long C O bond distance of the carbonyl ligand and the significantly short C=O bond length in the DMF ligand. When recrystallized from benzene/hexane under N₂, trans-[Mo(CO)(DMF)(dpe)(dpm)] was converted into trans-[Mo(CO)(N₂)(dpe)(dpm)].     

Conversion of alkynes and nitriles into organo and organonitrogenated species at group VI and VII dinitrogen-binding metal centers. Synthesis of some vinylidene and alkynyl complexes of rhenium

Summary The reactions of phenylacetylene and other alkynes [HCCCH₂OH, HCC(CH₂)₂OH, HCCCH₂CMe ₂CH₂COCH₃, HCCSiMe ₃ andMeCCSiMe ₃], in the presence of acetonitrile or benzonitrile, with the following complexes have been investigated usually at room temperature:trans-[Mo(N₂)₂ L ₄] (L=PMe ₂ Ph),cis-[Mo(N₂)₂(PMePh ₂)₄],cis-[W(N₂)₂ L ₄],trans-[ReCl(N₂)L ₄],mer-[ReCl(N₂)(PPh ₃)L₃] {L=P(OMe)₃}, [ReCl₂(N₂COPh)L₃] and [(⁵-MeC₅H₄)Mn(CO)₂(NCMe)]. Cyclic trimerization was the main reaction detected for phenylacetylene (except for the Mn complex), although dimers, products of hydrogenation and species derived from alkyne/nitrile coupling were also formed in smaller amounts; for the Mo- or W-systems, the total yields were below ca. 40% relative to the metal, but the Re-systems exhibited a modest catalytic activity. The other alkynes underwent, also in low yields, mainly dimerization, cyclic or linear trimerization, apart from, to a smaller extent, coupling reactions with the nitriles or hydrogenation. The alkynyl complexes [ReCl(CCPh) {P(O) (OMe)₂}(PPh ₃)L₂] and [ReCl(CCPh) {P(O)(OMe)₂}(NCMe)₂ L] were prepared by reaction ofmer-[ReCl(N₂)(PPh ₃)L₃] withPhCCH, in the absence and in the presence of NCMe, respectively, whereas the benzonitrile/dinitrogen complex [ReCl(N₂)(CNPh)L₃] was obtained either by reaction of that N₂-complex with NCPh or by the reaction of [ReCl₂(N₂COPh)L₃] with NCPh in the presence of NaOMe. The vinylidene compoundtrans-[Re(CNMe)(C=CHPh)(dppe)₂][BF₄] (dppe=Ph ₂PCH₂CH₂PPh ₂) was formed by reaction oftrans-[ReCl(CNMe)(dppe)₂] withPhCCH, in the presence of Tl[BF₄], which did not lead to the formation of detectable amounts of any alkyne-derived organic product.

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Umsetzung von Alkinen und Nitrilen zu Organo- und Organostickstoff-Spezies an distickstoffbindende Metallzentren der VI. und VII. Gruppe. Synthese einiger Vinyliden-und Alkinyl-Komplexe des Rhenium

Zusammenfassung Die Reaktionen von Phenylacetylen und anderen Alkinen [HCCCH₂OH, HCC(CH₂)₂OH, HCCCH₂CMe₂CH₂COCH₃, HCCSiMe₃ und MeCCSiMe₃] in Gegenwart von Acetonitril oder Benzonitril mit den folgenden Komplexen wurde wie üblich bei Raumtemperatur untersucht:trans-[Mo(N₂)₂ L ₄] (L=PMePh),cis-[Mo(N₂)₂(PMePh ₂)₄],cis-[W(N₂)₂ L ₄],trans-[ReCl(N₂)L ₄],mer-[ReCl(N₂)(PPh ₃)L₃] {L=P(OMe)₃}, [ReCl₂(N₂COPh)L₃] und [(⁵-MeC₅H₄)-Mn(CO)₂(NCMe)]. Die Hauptreaktion für Phenylacetylen war stets die cyclische Trimerisierung (mit Ausnahme des Mn-Komplexes), obwohl auch Hydrogenierungsprodukte und Spezies aus einer Alkin/Nitril-Kupplung in kleineren Mengen aufgefunden wurden; für die Mo- oder W-Systeme waren die Ausbeuten unter etwa 40% relativ zum Metall, die Re-Systeme zeigten eine schwache katalytische Aktivität. Die anderen Alkine gingen (auch in niedrigen Ausbeuten) hauptsächlich Dimerisierung, cyclische oder lineare Trimerisierung neben (in noch geringerem Maßstab) Kupplungs-reaktionen mit den Nitrilen oder Hydrogenierung ein. Die Alkinylkomplexe [ReCl(CCPh)-{P(O)(OMe)₂}(PPh ₃)L₂] und [ReCl(CCPh) {P(O)(OMe)₂}(NCMe)₂ L] wurden aus der Reaktion vonmer-[ReCl(N₂)(PPh ₃)L₃] mitPhCCH sowohl in Abwesenheit als auch in Gegenwart von NCMe gebildet, wohingegen der Benzonitril/Distickstoff-Komplex [ReCl(N₂)(NCPh)L₃] entweder aus der Reaktion dieses N₂-Komplexes mit NCPh oder über die Reaktion von [ReCl₂(N₂COPh)L₃] mit NCPh in Gegenwart von NaOMe gebildet wurde. Die Vinylidenverbindungtrans-[Re(CNMe)(C=CHPh)(dppe)₂] [BF₄] (dppe=Ph ₂PCH₂CH₂PPh ₂) wurde in der Reaktion vontrans-[ReCl(CNMe)-(dppe)₂] mitPhCCH in der Gegenwart von Tl[BF₄] gebildet, wobei keine detektierbaren Mengen irgendeines von Alkin abgeleiteten organischen Produkts entstanden.

     

A study of the protonation and alkylation oft-butyl isocyanide intrans-[M(CNBu-t 2(Ph2PCH2CH2PPh2)2] (M = Mo or W): Formation of carbyne-type complexes and theirtrans- tocis-isomerization

Summary Treatment of complexestrans-[M(CNBu-t)₂(dppe)₂][(1) M = Mo or W, dppe = Ph₂PCH₂CH₂PPh₂] with protic acid gives a mixture of the aminocarbyne complexestrans- pluscis-[M(CNHBu-t)(CNBu-t)(dppe)₂]⁺ (2) and the hydridocompounds [MH(CNBu-t)₂(dppe)₂]⁺ (3), whereas reaction with an alkylating agent (R⁺) appears to give the dialkylaminocarbyne compounds [M(CNRBu-t)(CNBu-t)(dppe)₂]⁺ (4) also as a mixture of thetrans andcis isomers.     

Influence of the trans Substituent on N2 Bonding in Iron(ii)–Phosphane Complexes: Structure,Synthesis, and Properties of the Monomeric Adducts trans-[FeXN2(depe)2]BPh4, X=Cl,Br

Not a dimer but a monomer was found in the X-ray structure analysis of the complex “trans-[{FeCl(depe)₂}₂(µ-N₂)](BPh₄)₂” (depe=Et₂PCH₂CH₂PEt₂). The complexes [FeXN₂(depe)₂]BPh₄ (X=Cl, Br; structure of the cation for X=Cl shown on the right) are much less stable than the analogous hydride compounds and undergo N₂ exchange at room temperature even in the solid state.     

On the Reactivity of the Platina‐β‐diketone [Pt2{(COMe)2H}2(μ‐Cl)2] Towards Ph2PCH2CH2CH2SOxPh (x = 0, 2)

The reaction of the electronically unsaturated platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) with Ph₂PCH₂CH₂CH₂SPh ( 2 ) leads selectively to the formation of the acetyl(chlorido) platinum(II) complex (SP‐4‐3)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 4 ) having the γ‐phosphinofunctionalized propyl phenyl sulfide coordinated in a bidentate fashion (κP,κS). In boiling benzene complex 4 undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex (SP‐4‐3)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SPh‐κP,κS)] ( 6 ). However, the reaction of 1 with the analogous γ‐diphenylphosphinofunctionalized propyl phenyl sulfone Ph₂PCH₂CH₂CH₂SO₂Ph ( 3 ) affords the acetyl(chlorido) platinum(II) complex (SP‐4‐4)‐[Pt(COMe)Cl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 5 ). In boiling benzene complex 5 undergoes a CO extrusion yielding (SP‐4‐4)‐[PtMeCl(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂] ( 8 ) whereas in presence of 1 the formation of the carbonyl complex (SP‐4‐3)‐[PtMeCl(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)] ( 7 ) is observed. Addition of Ag[BF₄] to complex 5 leads to the formation of the cationic methyl(carbonyl) platinum(II) complex (SP‐4‐1)‐[PtMe(CO)(Ph₂PCH₂CH₂CH₂SO₂Ph‐κP)₂][BF₄] ( 9 ). All complexes were characterized by microanalysis and NMR spectroscopy (¹H, ¹³C, ³¹P) and complexes 4 and 6 additionally by single‐crystal X‐ray diffraction analyses.     

Zweikern-Komplexe des Wolframs und Molybdäns mit zentraler {XMS2 MX}2+-Einheit (X=O,S) und S 2 2− -bzw. S 4 2− -Liganden

The synthesis and crystal structures of the compounds [PPh ₄]₂[W₂S₁₂]·0.5DMF, [PPh ₄]₂[W₂O₂S₁₀]·0.5DMF, [PPh ₄]₂[W₂S₁₀]··0.5DMF, [PPh ₄][NEt ₄][Mo₂OS₇]·CH₃CN, and [PPh ₄]₂[Mo₂O₂S₁₀] are reported.

     

Synthesis of the cyanamide-derived bis(cyanoimido) complexes trans-[M(NCN)2(Ph2PCH2CH2PPh2)2] (M = Mo or W) and crystal structure of the molybdenum compound

Reaction of cyanamide (NCNH₂) with trans-[M(N₂)₂(dppe)₂] (M = Mo or W, dppe = PH₂PCH₂CH₂PPh₂) leads to the formation of the bis(cyanoimido) complexes trans-[M(NCN)₂(dppe)₂]. The crystal structure of trans-[Mo(NCN)₂(dppe)₂] has been determined by an X-ray diffraction study.     

PREPARATION AND PROPERTIES OF DIAZENIDO,HYDRAZIDO(2-), AND HYDRIDO-HYDRAZIDO(2-) COMPLEXES OF TUNGSTEN. X-RAY PHOTOELECTRON SPECTROSCOPY OF DINITROGEN AND HYDRAZIDO(2-) COMPLEXES OF MOLYBDENUM AND TUNGSTEN

Abstract

Reactions of HBr with trans-[W(N₂)₂(dppe)PPh₂Me)₂] (1) (dppe = Ph₂CH₂CH₂PPh₂) result in protonation of coordinated N₂ but no formation of ammonia or hydrazine. The tungsten-containing product depends upon the reaction conditions: (i) in MeOH, the product formed is [WBr(NNH₂) (dppe)(PPh₂Me)₂]HBr₂ (2) which converts to the hydride, [WBr₂(H)(NNH₂(dppe)(PPh₂Me)](Br(3), with loss of phosphine in THF or CH₂Cl₂, (ii) in THF or CH₂Cl₂, the hydride (3) is formed directly. Reaction of 2 with Na₂CO₃ in MeOH results in the loss of HBr and the formation of the diazenido complex [WBr(NNH)(dppe)(PPh₂Me)₂] which reacts further with Na₂CO₃ in benzene under N₂ to lose HBr and form a mixture of 1 and trans-[W(N₂)(dppe)₂]. The reaction of 1 with aqueous HF forms [WF(NNH₂)(dppe)(PPh₂Me)₂]BF₄. The X-ray photoelectron spectra of trans-[M(N₂)₂ (dppe)₂], [MBr(NNH₂)(dppe)₂Br (M = Mo, W), [WCl(NNH₂)(dppe)₂]Cl, [WCl(N)(dppe)₂]Cl and [WCl(NH) (dppe)₂] are reported. In all of these complexes, nitrogen is in a highly reduced form.     

Synthesis of sulphonated aminomethylphosphines and some nickel(II), palladium(II), platinum(II) and rhodium(I) complexes. Crystal structure of [Et3NH][(Ph2PCH2)2 N(CH2)2SO3]

Summary Aminoalkanesulphonic acids H₂N(CH₂) _n SO₃H, (n = 1, 2 or 3) react with phosphonium salts [R₂P(CH₂OH)₂]Cl (R = Ph or Cy, Cy = cyclohexyl) in the presence of Et₃N to give the sulphonated aminomethylphosphines [Et₃NH] [(R₂PCH₂)₂N(CH₂) _n SO₃] (R = Ph, n = 1, 2 or 3; R = Cy, n = 1). The single crystal X-ray structure of [Et₃NH] [(Ph₂PCH₂)₂N(CH₂)₂SO₃] has been determined. Some Ni^II, Pd^II, Pt^II and Rh^I complexes of the phosphines have been prepared.     

Synthesis of bridged and linked ruthenium and osmium carbonyl clusters containing a [Au2(Ph2PCH2CH2PPh2)]2+ unit. The crystal and molecular structures of Ru5C(CO)14Au2(Ph2PCH2CH2PPh2) and {Os4H3(CO)12}2Au2(Ph2PCH2CH2PPh2)

Treatment of Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂ with one equivalent of the [Ru₅C(CO)₁₄]²⁻ dianion in the presence of TlPF₆ gives Ru₅C(CO)₁₄Au₂(Ph₂PCH₂CH₂PPh₂) (1) in good yield and the [{Ru₅C(CO)₁₄}₂Au₂(Ph₂PCH₂CH₂PPh₂)]²⁻ (2) anion in low yield. Complex 2 becomes the major product if 2 equivalents of [Ru₅C(CO)₁₄]²⁻ are used. Reaction of [Au₂(Ph₂PCH₂CH₂PPh₂)Cl₂] with 3 equivalents of [H₃Os₄(CO)₁₂]⁻ anion in the presence of TlPF₆ affords {H₃Os₄(CO)₁₂}₂Au₂(Ph₂PCH₂CH₂PPh₂) (3) in reasonable yield. X-ray diffraction studies of 1 and 3 show that they contain the [Au₂(Ph₂PCH₂CH₂PPh₂)]²⁺ fragment in different coordination modes.     

Ligand behaviour of P-functionally substituted organotin halides: palladium(II) and platinum(II) complexes with Ph2PCH2CH2SnCl3

The P-functional organotin chloride Ph₂PCH₂CH₂SnCl₃ reacts with [(COD)MCl₂] and trans-[(Et₂S)₂MCl₂] (M=Pd, Pt) in molar ratio 1:1 to the zwitterionic complexes [(COD)M⁺(Cl)(PPh₂CH₂CH₂Sn⁻Cl₄)] (1: M=Pd; 2: M=Pt) and trans-[(Et₂S)₂M⁺(Cl)(PPh₂CH₂CH₂Sn⁻Cl₄)] (3: M=Pd; 4: M=Pt). The same reaction with [(COD)Pd(Cl)Me] yields under transfer of the methyl group from palladium to tin the complex [(COD)M⁺(Cl)(PPh₂CH₂CH₂Sn⁻MeCl₃)] (5) which changes in acetone into the dimeric adduct [Cl₂Pd(PPh₂CH₂CH₂SnMeCl₂·2Me₂CO)]₂ (6). In molar ratio 2:1 Ph₂PCH₂CH₂SnCl₃ reacts with [(COD)MCl₂] to the complexes [Cl₂Pd(PPh₂CH₂CH₂SnCl₃)₂] (7: M=Pd, mixture of cis/trans isomer; 8: M=Pt, cis isomer). In a subsequent reaction 8 is transformed in acetone into the 16-membered heterocyclic complex cis-[Cl₂Pt(PPh₂CH₂CH₂)₂SnCl₂]₂ (9). trans-[(Et₂S)₂PtCl₂] and Ph₂PCH₂CH₂SnCl₃ in molar ratio 1:2 yields the zwitterionic complex [(Et₂S)M⁺(Cl)(PPh₂CH₂CH₂SnCl₃)(PPh₂CH₂CH₂Sn⁻Cl₄)] (10). The results of crystal structure analyses of 1, 3, 6, 9 and of the adduct of the trans-isomer of 7 with acetone (7a) are reported. ³¹P- and ¹¹⁹Sn-NMR data of the complexes are discussed.     

Transition metal complexes with bidentate ligands spanning trans-positions. IV. Preparation and properties of some rhodium and iridium complexes of 2,11-bis(diphenylphosphinomethyl)benzo [c]phenanthrene

The bidentate phosphine 2,11-bis(diphenylphosphinomethyl)benzo [c]phenanthrene ( 1 ) has been used to prepare the mononuclear, square planar complexes trans-[MX(CO)( 1 )] and trans-[M(CO)(CH₃CN)( 1 )][BF₄] (M = Rh, Ir; X = Cl, Br, I, NCS). It is found that the tendency of these complexes to form adducts with CO, O₂ and SO₂ is significantly lower than that of the corresponding Ph₃P complexes. The oxidative-addition reactions of complexes trans-[IrX (CO) ( 1 )] with hydrogen halides give the six-coordinate species [IrHX₂(CO) ( 1 )]. The complexes [IrH₂I (CO) ( 1 )] and [IrH₂L (CO) ( 1 )] [BF₄] (L = CO and CH₃CN) have been obtained from hydrogen and the corresponding substrates. The model compounds trans-[MCl (CO) (Ph₂PCH₂Ph)₂] (M = Rh, Ir), trans-[Ir (CO) (CH₃CN) (Ph₂PCH₂Ph)₂] [BF₄], [IrHCl₂(CO)(Ph₂PCH₂Ph)₂] and [IrH₂(CO)₂(Ph₂PCH₂Ph)₂] [BF₄] have been prepared and their special parameters are compared with those of the corresponding complexes of ligand 1 . The influence of the static requirements of this ligand on the chemistry of its rhodium and iridium complexes is discussed.     

Darstellung und Röntgenstrukturanalyse von 26 Thiomolybdato- bzw. Thiowolframato-und eines Selenowolframato-Komplexes

Summary The preparation and characterization by X-ray structure analysis of the following chalcogenometalato complexes are reported: 1: [(Ph ₃P)₂N]₂(NEt ₄)[Fe(WS₄)₂]·2MeCN; 2: [(Ph ₃P)₂N]₂(NEt ₄)[Cu(WS₄)₂]·2MeCN; 3: [(Ph ₃P)₂N]₂(NEt ₄)[Ag(MoS₄)₂]·MeCN; 4: [(Ph ₃P)₂N]₂(NEt ₄)[Ag(WS₄)₂]·MeCN; 5: (PPh ₄)₂[Hg(WS₄)₂]; 6: (PPh ₄)₂[Au₂(WOS₃)₂]; 7: (PPh ₄)₄[Pb₂(MoS₄)₄]; 8: (PPh ₄)₄[Pb₂(WS₄)₄]; 9: (NEt ₄)₂[Fe(WS₄)₂(H₂O)₂]; 10: [Fe(DMSO)₆][Cl₂Fe(MoS₄)]; 11: [Fe(DMSO)₆][Cl₂Fe(MoOS₃)]; 12: (PPh ₄)(NMe ₃CH₂ Ph)[Cl₂Fe(WS₄)]; 13: [Fe(DMF)₆][Cl₂Fe(WS₄)]; 14: (PPh ₄)₂[Cl₂Fe(WS₄)]; 15: (PPh ₄)₂[Cl₂Fe(WS₄)]·2 CH₂Cl₂; 16: (PPh ₄)₂[NCCu(MoS₄)]; 17: (PPh ₄)₂[NCAg(MoS₄)]; 18: (PPh ₄)₂[NCAg(WS₄)]; 19: (PPh ₄)₂[Cu₃Cl₃(MoOS₃)]; 20: (PPh ₄)₂[Cu₃Br₃(MoS₄)]·MeCN; 21: (PPh ₃)₃Cu₂(MoOS₃)·0.8 CH₂Cl₂; 22: (PPh ₃)₃Cu₂(WOS₃)·0.8 CH₂Cl₂; 23: {Cu₃MoS₃Br}(PPh ₃)₃O·0.5Me ₂CO; 24: (PPh ₃)₃Ag₂(WSe₄)·0.8 CH₂Cl₂; 25: [(Ph ₃P)₂N]₂(NEt ₄)₂[Fe₂S₂(WS₄)₂]·3MeCN; 26: (PPh ₄)₂[MoO(MoS₄)₂]; 27: (PPh ₄)₂[Br₂Fe(WOS₄)]·DMF.

     

Synthesis of trans-[Re(NO)2-(Ph2PCH2CH2PPh2)2][BF4], a formal dinitrosyl complex of rhenium(-I) and its protic denitrosylation. X-Ray structure of trans-[ReF(NO)-(Ph2PCH2CH2PPh2)2][BF4]

Treatment of a THF solution of trans-[ReCl(N₂)(dppe)₂] (dppe = Ph₂PCH₂CH₂PPh₂) with NO, in the presence of Tl[BF₄], forms trans-[Re(NO)₂(dppe)₂][BF₄], a rare formal 20-electron d⁸-rhenium nitrosyl complex which, by reaction with HX (X = BF₄, Cl or HSO₄), gives trans-[ReF(NO)(dppe)₂][BF₄] (2) (the X-ray structure of which is reported) or trans-[ReX(NO)(dppe)₂]X (3, X = Cl or HSO₄), respectively, as well as nitrous oxide.     

Synthesis and crystal structure of [MoH3(CCBut)(Ph2PCH2CH2PPh2)2], a trihydrido-alkynyl complex

Reaction of Bu^tCCH with trans-[Mo(N₂)₂(dppe)₂] (dppe = Ph₂PCH₂CH₂PPh₂) gives [MoH₃(CCBu^t)(dppe)₂], whose X-ray structure is reported.     

Photochemical reduction of carbon dioxide to formate in the coordination sphere of MoH4(PH2PCH2CH2PPh2)2

UV, IR, and NMR spectra of photolysis products obtained by irradiation of MoH₄(Ph₂PCH₂CH₂PPh₂)₂ (1) in an atmosphere of CO₂,¹³CO₂, or C¹⁸O₂ were studied. In the coordination sphere of1, photochemical reduction of carbon dioxide occurs, yielding products of formate type. Treatment of photoproducts with acids affords formaldehyde.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2043–2045, October, 1995.The author is grateful to A. P. Borisov and V. D. Makhaev for providing a sample of MoH₄(Ph₂PCH₂CH₂PPh₂)₂.     

Preparation and crystallographic characterization of Pd(II) complexes containing imidobis(diphenylthiophosphinato) ligand

The reactions of PdCI₂(L-L) [L-L = Ph₂PCH₂PPh₂(dppm), Ph₂PCH₂CH₂PPh₂(dppe) and Ph₂PCH₂CH₂CH₂PPh₂(dppp)] with equivalent amount of (Ph₂P(S)NHP(S)Ph₂)(dppaS₂) gave the complexes [Pd(L-L)(dppaS₂-H)]ClO₄ [L-L = dppm (1), dppe (2), dppp (3)]. The different synthetic route was used for complex 2 by using of Pd(dppe)Cl₂ and K[N(PSPh₂)₂] as starting materials (2a). All of these complexes have been characterized ³¹P{¹H} NMR, IR and elemental analyses. The complexes 2, 2a and 3 were crystallographically characterized. The coordination geometry around the Pd atoms in these complexes distorted square planar. Six membered dppaS₂-H rings are twist boat conformations in three complexes.     

Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine

New complexes of the formulae K₃[RhL ₃]·2 H₂O, [PdL]·H₂O and [M(LH₂)Cl₂] [whereM = Pd, Pt andLH₂ = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and¹H-NMR spectroscopy.

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Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)

Zusammenfassung Neue Komplexe der allgemeinen Formeln K₃[RhL ₃]·2H₂O, [PdL]·H₂O und [M(LH₂)Cl₂] mitM = Pd, Pt undLH₂ = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und¹H-NMR-Spektroskopie charakterisiert.

     

[Boranato-bis(dimethylphosphonium-methylid)]-Komplexe der do- und d10-Metalle: Li,Be, Mg,Zn, Cd,Hg, Al und Ga

Dehydrohalogenation and metallation of boranato-bis-trimethylphosphonium salts (1), using two equivalents of a lithiumalkyl in tetrahydrofuran, leads to a solvated organolithium reagent H₂B[(CH₃)₂PCH₂]₂Li (3) which can be converted into a 1:1n1-complex with tetramethylethylenediamin (4).3 reacts with anhydrous metal(II) halides to form spirocyclic coordination compounds of the type H₂B[(CH₃)₂PCH₂]₂ M[CH₂P(CH₃)₂]₂BH₂ (5–9,M=Be, Mg, Zn, Cd, Hg). The reaction of [(CH₃)₃PBH₂P(CH₃)₃]Br (1) with lithium tetramethylmetalates Li[M(CH₃)₄],M=Al, Ga, on heating in the absence of a solvent affords the metallocycles H₂B[(CH₃)₂PCH₂]₂ M(CH₃)₂ (10, 11) with evolution of methane. The products can be sublimed from the reaction mixture. The proposed structures of the new compounds, with tetrahedrally coordinated central atoms and strong covalent metal-carbon interactions, are supported by mass, IR and¹H,⁷Li,¹¹B,¹³C, and³¹P NMR spectra. Compound9 represents a rare case of a tetracoordinate organomercurial, compound5 is the first nonionic tetraalkylberyllate.