Electrochemistry of coordination compounds: Part XIV. Polarographic behaviour of d8 ruthenium nitrosyl complexes

The voltammetric behaviour of the new complex, [Ru(NO)(Ph₂PCH₂CH₂CH₂PPh₂)₂]⁺, has been studied in 1,2-dimethoxyethane and the results compared with those obtained in the analogous reduction of [Ru(NO)(Ph₂PCH₂PPh₂)₂]⁺. The reduction proceeds in two reversible, one-electron steps. Stepwise reduction of these cationic complexes leads to two reversible, one-electron steps. Stepwise reduction of these cationic complexes leads to anionic complexes with formal oxidation number (?II) through the intermediate state which, in the case of Ph₂PCH₂CH₂PPh₂ ligand, is unstable and decays via a disproportionation pathway. A reduction-oxidation mechanism accounting for the chemical and electrochemical results is proposed.     

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.     

Mixed ligand transition metal complexes of tertiary phosphines and 5-phenyl-l,3,4-oxadiazole-2-thione

Transition metal complexes containing two types of ligands: 5-phenyl-1,3,4-oxadiazole-2-thione ion (L) and tertiary phosphines, have been prepared. The complexes, [ML₂A₂] [M = Pd or Pt; A = PPh₃ or Ph₂PCH₂CH₂P(O)Ph₂] and [ML₂B] (M = Co, Ni, Pd or Pt; B = Ph₂PCH₂PPh₂ or Ph₂PCH₂CH₂PPh₂), were characterized by elemental analysis, molar conductance, i.r., u.v.–vis., ³¹P-n.m.r., magnetic susceptibility measurements and mass spectra.     

Synthesis and characterization of silver(I) complexes with N‐thiophosphorylated thiobenzamide or thiourea and phosphines

A reaction of the potassium salts of RC(S)NHP(S)(OiPr)₂ (R = PhNH, HL ^I; Ph, HL ^II) with a mixture of AgNO₃ and Ph₂P(CH₂)_{1 − 3}PPh₂ or Ph₂P(C₅H₄FeC₅H₄)PPh₂ in aqueous EtOH/CH₂Cl₂ leads to [Ag₂(Ph₂PCH₂PPh₂)₂L^INO₃] ( 1 ), [Ag{Ph₂P (CH₂)₂PPh₂}L^I,II] ( 2, 6 ), [Ag{Ph₂P(CH₂)₃PPh₂}L^I,II] ( 3, 7 ), [Ag{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^I,II] ( 4, 8 ), and [Ag₂(Ph₂PCH₂PPh₂)L^II₂] ( 5 ) complexes. The structures of these compounds were investigated by ¹H and ³¹P{¹H} NMR spectroscopy and elemental analyses. It was established that the binuclear complexes 1 and 5 are luminescent in the solid state at ambient conditions. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:386–391, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20627     

Neutral and cationic orthopalladated ( ) complexes ( = phenylazophenyl, dimethylbenzylamine, 8-methylquinoline, 2-methoxy-3-N,N-dimetrylaminopropyl)

By reacting [Pd( )(μ-Cl)]₂ with AgClO₄ in NCMe, the corresponding cationic complexes [Pd( )(NCMe)₂]ClO₄ ( = phenylazophenyl-C²,N¹; dimethylbenzylamine-C²,N; 8-methylquinoline-C⁸,N) can be obtained. Solutions containing the cations [Pd( )(S)₂]⁺ are obtained when the reaction is carried out in tetrahydrofuran or acetone (S). The treatment of these solutions with bidentate ligands (L—L) (Ph₂PCH₂PPh₂,Ph₂PNHPPh₂ or Ph₂PCH₂PPh₂CHC(O)Ph) gives the mononuclear [Pd( )(L3l)]ClO₄ complexes, with L3l acting as a chelate ligand. On the other hand [Pd( (μ-Cl)]₂ reacts with L3l (Ph₂PCH₂PPh₂, Ph₂PNHPPh₂) yielding [Pd( )Cl(L3l)] with L3l acting as monodentate. The reactions between [Pd( )(NCMe)₂]ClO₄ and 2,2′-bipyrimidyl give rise to the formation of the mononuclear [Pd( ) (bipym)]ClO₄ or binuclear [Pd₂( )₂(μ-bipym)](ClO₄)₂, [( )Pd(μ-bipym)Pd( )](ClO₄)₂ derivatives. Finally [Pd( )Cldppm] (dppm = Ph₂PCH₂PPh₂) react with NaH producing the neutral complexes [Pd( )(ddppm)] (ddppm = Ph₂PCHPPh₂) which by reaction with HCl lead again to the starting materials [Pd( )Cl(dppm)].     

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.     

Ditertiary phosphine complexes of (ν-allyl)dicarbonylmolybdenum(II) and -tungsten(II)

Compounds of the type [XM(CO)₂(ν-allyl)L₂] (where X = Cl and Br; M = Mo and W; L₂ = Ph₂PCH₂PPh₂ and Ph₂ PCH₂CH₂PPh₂) have been prepard from the corersponding MeCN complexes. The spectral properties of these compounds and the effects of chelate rign size on ³¹P coordination shifts and J(¹⁸³W—³¹P) have been investigated.     

New cationic and anionic tetracoordinate nickel(I) complexes

Summary The preparation, structural study and chemical behaviour of new cationic, monoanionic and dianionic tetracoordinate nickel(I) complexes of the types: [NiL₄][BPh₄] (L=PPh₃, AsPh₃ or SbPh₃), [PR₄][NiX₂L₂] (X=Cl, Br or I; L=PPh₃, AsPh₃ or SbPh₃ and [PR₄]⁺=PPh₄, Ph₃PCH₂Ph or Ph₃PEt) and [PR₄]₂[NiX₃L] (X=Cl, Br or I; L=PPh₃ and [PR₄]⁺=PPh₄ or PPh₃CH₂Ph) are described.     

Complexes of (ω-diphenylphosphinoalkyl)diphenylphosphine sulfides with silver nitrate in pyridine

The behavior of the phosphine-phosphine sulfide complexes of silver, [Ph₂P(S)(CH₂) _n PPh₂] _m ·AgNO₃ (n=2 or 4;m=1 or 2), in pyridine was studied. Dissolution of the 1:1 complexes in pyridine leads to destruction of their dimeric structures Ag₂[Ph₂P(S)(CH₂) _n PPh₂]₂(NO₃)₂ (A) to form the complexes Agp_y ⁺−P(Ph₂)(CH₂) _n Ph₂P=S and Agp_y ⁺−S=PPh₂(CH₂) _n PPh₂. The solid complexes isolated from pyridine restore dimeric structure A. According to the data of X-ray diffraction analysis, the 1:2 complex isolated from pyridine has the structure [S=P(Ph₂)(CH₂)₂(Ph₂)P−(NO₃)Ag(Py)−P(Ph₂) (CH₂)₂(Ph₂)P=S]Py. According to the data of IR spectroscopy, dissolution of this complex in chloroform leads to the formation of the dimeric structure Ag₂Ph₂P(S)(CH₂)₂PPh₂]₄(NO₃)₂. Deceased. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1751–1758, September, 1998.     

Iridium nitrosyl complexes of 2-aminophenol derivatives

Summary The synthesis and characterisation of products obtained by the interaction between [Ir(NO)(MeCN)₂(PPh₃)₂]²⁺ and 2-aminophenol derivatives are reported. Tetracoordinate d⁸complexes of the type Ir(NO)(2-ap)(PPh₃) and pentacoordinate d complexes₆of the type [Ir(2-ap)(PPh₃)₃]⁺ where 2-ap=2-aminophenol, 2-amino-4-nitrophenol, 2-amino-5-methylphenol, 2-3-aminonaphthol and 2-amino-4-methylphenol are obtained. The Ir(NO)(PPh₃)₃ complex is always present as a byproduct. Physical properties, i.r. spectra and conductivity data of the complexes are tabulated. Reaction schemes for the formation of the three complexes are proposed and discussed.     

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.     

Cyanoalkyl complexes of transition metals . : II. Preparation and properties of some platinum complexes containing phosphorus as a donor atom

cis-PtCl(CH₂CN)(PPh₃)₂ was obtained by the reaction of Pt(PPh₃)₄ with ClCH₂CN in acetone. A solution of Pt(PPh₃)₄ and ClCH₂CN in benzene was heated under reflux to give trans-PtCl(CH₂CN)(PPh₃)₂. The reaction of the trans-isomer with Br^?, I^?, Ph₂PCH₂CH₂ PPh₂, Ph₂PCH₂CH₂AsPh₂ and cisPh₂PCHCHPPh₂ has been examined. The trans-influence of a ligand trans to the CH₂CN group seems to be indicated by the ²J(PtH) of the CH₂CN protons. The τ values of trans-PtX(CH₂CN)(PPh₃)₂ and PtX(CH₂ CN)(PP) (X = Cl, Br, I) are related by a linear function.     

Rhodium and iridium complexes containing the anion of 1-phenyl-3-methyl-4-benzoyl- pyrazolone-5, a sophisticated analogue of β-diketones

Several (diolefin)M(A) complexes (M = Rh, Ir) were prepared, where AH is 1-phenyl-3-methyl- 4-benzoylpyrazolone-5, a very stable asymmetric analogue of acetylacetone. In these complexes the diolefin could be replaced by one mole of (Ph₂PCH₂CH₂)₂, two of CO or of PPh₃, or three of CNBu^t, while 1,10-phenanthroline displaced the chelating ligand to yield [(cyclooctadiene)Rh(phen)]⁺ (A)^?. Some compounds X?Y (X?Y = iodine or MeI) added oxidatively yielding the corresponding trivalent species. Using ³¹P NMR spectra the presence of the expected steric isomers was detected in (Ph₃P)(CO)Rh(A) and in (Ph₃P) (CO)Rh(A)(X)(Y).     

Ionic Platinum(II)–Imidobis(diphenylthiophosphinato) Complexes: Preparation,Structure, and Thermal Behavior

The PPh₂P(S)NHP(S)PPh₂ (dppaS₂) ligand reacts with the starting complexes PtCl₂(L-L) (L-L = Ph₂PCH₂PPh₂), (dppm), Ph₂PCH₂CH₂PPh₂ (dppe), Ph₂PCH₂CH₂CH₂PPh₂ (dppp), and NaClO₄·H₂O. Final products are monomeric complexes, and their formulas are [Pt(L-L)(dppaS₂-H)] [(L-L = dppm(1), dppe(2), dppp(3)]. All of these have been characterized by ¹H, ¹³C^,31{P¹H} NMR, FTIR, and elemental analysis. These complexes were also examined by TGA, DTA, and DSC analysis. Complexes 2 and 3 were crystallographically characterized.     

Platinum group metal functionalized phosphine complexes. Part 2. Phosphinoamide rhodium(I), iridium(I), palladium(II) and platinum(II) complexes

Summary Rhodium(I), iridium(I), palladium(II) and platinum(II) complexes of the phosphinoamide ligands, Ph₂PCH₂CONHR (R = H, HDPA; Me, MDPA; Ph, PDPA) were prepared and characterized by using conductivity data, i.r., ¹H and ³¹P(H) n.m.r. spectral data. Reaction of the ligands with MCl(PPh₃)₃ and MCl(CO)(PPh₃)₂ (M = Rh, Ir) in CH₂Cl₂ under reflux lead to the formation of MCl(PPh₃)₂ [Ph₂PCH₂C(O)NHR] and MCl(CO)(PPh₃)[Ph₂PCH₂–C(O)HNR] respectively. The reaction of either K₂MCl₄ or cis-MCl₂(PPh₃)₂ affords complexes of the type cis-MCl₂[Ph₂PCH₂C(O)NHR]₂ (M = Pd, Pt). A similar product results even from the reaction of phosphinoamides with cis-platin. Possible structures are proposed for the complexes based on their physicochemical data     

The electrochemistry of organotransition-metal complexes : II. Formation and reactivity of the radical cations [trans-Fe(CO3(PR3)2]+ and [Fe(CO)3 (Ph2 PCH2 CH2 PPh2)]+

[Fe(CO)₃ L₂] (L = PPh₃, PPh₂Me, P(OPh)₃ or P(NMe₂)₃; L₂ = Ph₂ PCH₂ CH₂ PPh₂⁺) undergo reversible one-electron oxidations to give the radical cations [Fe(CO)₃L₂]⁺ which have been studied by IR and ESR spectroscopy.     

Transition Metal Complexes with Bidentate Ligands Spanning trans-Positions. VIII. The reactions of the nucleophile trans-[RuCl(NO)(1)] (1 = 2,11-bis(diphenylphosphinomethyl)benzo[c]-phenanthrene) with carbon monoxide and the phosphite ligand (2) (2 = 1-ethyl-3,5,8-trioxa-4-phosphabicyclo (2.2.2)octane)

The preparation of the nucleophile trans-[RuCl(NO)( 1 )], where 1 is the bidentate ligand Ph₂PCH₂C₁₈CH₂PPh₂, and of the five-coordinate species [RuCl(CO)(NO)( 1 )], [RuCl(CO)(NO)(Ph₂PCH₂Ph)₂] and [RuCl(NO)( 2 )( 1 )] are reported. The crystal structure of [RuCl(CO)(NO)( 1 )] shows that the coordination around the metal atom is distorted trigonal bipyramidal with the phosphorus atoms in axial positions. The Ru? N? O bond angle is 142.8°. ¹H- and ³¹P-NMR. and \documentclass{article}\pagestyle{empty}\begin{document}$ \tilde \nu $\end{document}_NO IR.-data for the above complexes are reported and related to the coordination geometry.     

Metal Ions in Biological Systems,Volume 4. Metal Ions as Probes; : edited by Helmut Sigel,Marcel Dekker,New York, 1974, xii + 261 pages, $24.75.

Trends in ³¹P NMR coordination shifts for the complexes M(CO)₃BrL₂, [M(CO)₃L₂(NCMe)]⁺, MeC₅H₄Mn(CO)L₂ and [MeC₅H₄Mn(CO)₂]₂L₂ (M = Mn and Re;L₂ = Ph₂PCH₂PPh₂, Ph₂PCH₂CH₂PPh₂ and Ph₂PCH₂CH₂AsPh₂) are discussed.     

Synthesis and characterization of nickel(II) maltolate complexes containing ancillary bisphosphine ligands

Cationic nickel(II) complexes containing chelating O,O′-donor maltolate or ethyl maltolate ligands in conjunction with bidentate bisphosphine ligands Ph₂P(CH₂) _n PPh₂ were prepared by a one-pot reaction starting from nickel(II) acetate, bisphosphine, maltol (or ethyl maltol), and trimethylamine, and isolated as their tetraphenylborate salts. An X-ray structure determination of [Ni(maltolate)(Ph₂PCH₂CH₂PPh₂)]BPh₄ shows that the maltolate ligand binds asymmetrically to the (slightly distorted) square-planar nickel(II) center. The simplicity of the synthetic method was extended to the synthesis of the known platinum(II) maltolate complex [Pt(maltolate)(PPh₃)₂]BPh₄ which was obtained in high purity.