Synthesis of the pentacarbonyl(chalcocarbonyl)chromium(0) complexes,Cr(CO)5(CX) (X = S,Se)

The arene complexes, (η⁶-C₆H₆)Cr(CO)₂(CX) (X = S, Se), react with excess CO gas under pressure in tetrahydrofuran at about 60° C to produce the Cr(CO)₅(CX) complexes in high yield. The IR and NMR (¹³C and ¹⁷O) spectra of these complexes are in complete accord with the expected C_4v molecular symmetry. Like the analogous W(CO)₅(CS) complex, both compounds react with cyclohexylamine to give Cr(CO)₅(CNC₆H₁₁). However, while W(CO)₅(CS) undergoes stereospecific CO substitution with halide ions (Y^? to form trans-[W(CO)₄(CS)Y]^?, the two chromium chalcocarbonyl complexes apparently undergo both CO and CX substitution to afford mixtures of [Cr(CO)₅Y]^? and trans-[Cr(CO)₄(CX)Y]^?.     

Bis(dimethylphosphino)methane (dmpm) complexes of iron,molybdenum and chromium: X-ray crystal structures of FeCr(CO)6(μ-dmpm)2 and Fe2(CO)4(μ-CO)(μ-dmpm)2

The photolysis of Fe(η¹-dmpm)(dmpm)₂ [dmpm = bis(dimethylphosphino) methane) with Cr(CO)₆ and Fe(CO)₅ under UV irradiation produces FeCr(CO)₆(μ-dmpm)₂, Fe₂(CO)₆(μ-CO)(μ-dmpm) and Fe₂(CO)₄(μ-CO)(μ-dmpm)₂ respectively. The interaction of Mo(CO)₃(MeCN)₃ and (C₇H₈)Cr(CO)₃ with dmpm produces Mo₂(CO)₆(μ-dmpm)₃ and cis-Cr(CO)₂(dmpm)₂ respectively. The X-ray crystal structure of FeCr(CO)₆(μ-dmpm)₂ shows the molecule to contain a trigonal bipyramidal Fe(CO)₃P₂ unit plus a square pyramidal Cr(CO)₃P₂ unit held closely together by the methylene bridges of the dmpm ligands with steric compression between the CO groups causing distortions from ideal geometry in each case. The Cr … Fe distance is 3.111(6) Å and there seems to be little structural evidence of any form of interaction between the 16e Cr(O) centre and the Fe-containing unit. The structure of Fe₂(CO)₄(μ-CO)(μ-dmpm)₂ contains a symmetrical μ₂-carbonyl and a single bond between the two symmetry related (m) iron atoms. The Fe … Fe distance is 2.719(4) Å.     

Photochemical studies of M(CO)6 (M = Cr,Mo, W) at low temperature in solution. Infrared spectra of M(CO)5 (solvent) (solvent = methylcyclohexane,methylene chloride) and W(CO)5L (L = aromatic hydrocarbon)

The infrared spectra of M(CO)₅(MCH) (MCH = methylcyclohexane; M = Cr, Mo, W), formed by 366 nm irradiation of M(CO)₆ at ?78°C in rigorously purified methylcyclohexane, are reported. The previously reported spectrum of “W(CO)₅” at low temperature in methylcyclohexane/isopentane solution is attributed to W(CO)₅(impurity), where the impurity is probably an aromatic or olefinic hydrocarbon. Spectra in methylene chloride solution are also discussed. The photochemical reactions of W(CO)₆ with aromatic hydrocarbon ligands in methylcyclohexane solution were also studied at ?78°C in a low temperature infrared cell. Irradiation (366 nm) of W(CO)₆ at ?78°C in rigorously purified methylcyclohexane solution containing approximately 5% (v/v) toluene, benzene, mesitylene, biphenyl, or p-xylene initially produces the complex W(CO)_5? (MCH). In the presence of the aromatic hydrocarbon, this complex is unstable and it decomposes in a dark reaction to give a complex which has an infrared spectrum typical for a C_4v M(CO)₅X molecule. It is proposed that the product of the dark reaction is W(CO)₅(aromatic), formed by reaction of W(CO)₅(MCH) with the aromatic ligand in solution. The infrared spectra of the W(CO)_5? (aromatic) complexes are different from the spectra previously reported for these complexes. It is shown that the spectra previously reported for W(CO)_5? (aromatic) are actually attributable to W(CO)₅(hexane) (hexane was the solvent used in the previous study); these spectra were probably obtained before W(CO)₅(hexane) had time to react with the aromatic hydrocarbon.     

Darstellung,Strukturen und Eigenschaften von Tris-hexamethyl-trisila-tetraphospha-nortricyclen-bis-chromtricarbonyl [P4(Sime2)3]3[Cr(CO)3]2

Preparation, Structures, and Properties of Tris-hexamethyl-trisila-tetraphospha-nortricyclene-bis-chromiumtricarbonyl [P₄(Sime₂)₃]₃[Cr(CO)₃]₂ Hexamethyl-trisila-tetraphospha-nortricyclene P₄(Sime₂)₃ 1 reacts with C₆H₆Cr(CO)₃ or (CHT)Cr(CO)₃ (CHT ? Cycloheptatriene) under formation of [P₄(Sime₂)₃]₃[Cr(CO)₃]₂ 3 (red crystals), in which each of the Cr atoms is attached to one P atom of a P₃ ring of the three molecules 1 . 3 can also be prepared by heating a solution of P₄(Sime₂)₃Cr(CO)₅ in benzene or THF up to 120–1307deg;C. The compound 3 crystallizes in an orthorhombic and a hexagonal form, the latter being stabilized by one mole toluene. As revealed by single crystal investigations, the symmetry ¯6, distances and angles are nearly unchanged. The o-form corresponds to a face centered cubic packing of the molecules, whereas the h-form is hexagonal close packed.     

Pentacarbonyl(4‐phenylpyridine)­tungsten(0) and pentacarbonyl(2‐phenylpyridine)chromium(0)

In penta­carbonyl(4‐phenyl­pyridine)­tungsten(0), [W­(C₁₁H₉N)(CO)₅], the mol­ecules have mm site symmetry and the pyridine ligand, with m symmetry, is completely planar. In penta­carbonyl(2‐phenyl­pyridine)­chromium(0), [Cr(C₁₁­H₉N)(CO)₅], the mol­ecules are in general positions and the phenyl and pyridine rings of the ligand are twisted by 67.7 (3)° with respect to one another by rotation about the C—C bond joining them. In both compounds, the axial M—C_carbonyl bond trans to the M—N_ligand bond is significantly shorter than the equatorial M—C_carbonyl bonds.     

Carbonyl complexes of 1,2,4-triazoles : II. The crystal structure of pentacarbonyl-4-methyl-1,2,4-triazolechromium(0), Cr(CO)5(C3H3H5). Chromium-to-triazole π-bonding

The crystal structure of pentacarbonyl-4-methyl-1,2,4-triazolechromium [Cr(CO)₅(C₃N₃H₅)] has been determined by single-crystal X-ray techniques. The compound crystallizes in the space group Pbca with a 10.899(2), b 17.572(2), c 11.877(2) Å and Z = 8. The compound consists of monomeric units in which the chromium atom is coordinated octahedrally to five CO groups and one monodentate coordinating 4-methyl-1,2,4-triazole ligand (CrN 2.111(2) Å). Full matrix least-squares refinement resulted in a final R = 0.025 (R_w = 0.0324). There appears to be no or little π-interaction between the triazole ligand and the chromium atom.     

Cyclopropene als komplexliganden. Cyclopropenthionkomplexe mit den gruppen Cr(CO)5 und (C5H5)Mn(CO)2

Diphenylcyclopropenethione and dithienylcyclopropenethione react with (acetonitrile)₃Cr(CO)₃ under mild conditions with formation of (C₃Ph₂S)Cr(CO)₅ and [C₃(C₄H₃S)₂S]Cr(CO)₅, respectively. Using (η⁵-C₅H₅)(THF)Mn(CO)₂ and diphenylcyclopropenethione a different type of complex with the stoichiometry (C₃Ph₂S)₂Mn(C₅H₅)(CO)₂ is obtained. A structure with a ligand containing two S bridges is proposed.     

Cr(CO)5(CNCN), a complex in which the coordinated CN group of isocyanogen binds and vibrates like a CO ligand

The IR and Raman spectra have been determined of the products formed by low-temperature (−20°C) replacement of 2-MeTHF (2-methyltetrahydrofuran) in photochemically produced Cr(CO)₅(2-MeTHF) by isocyanogen, CNCN. The IR spectra are interpreted in terms of the formation of an isonitrile and a nitrile complex, Cr(CO)₅(CNCN) and Cr(CO)₅(NCNC). A detailed study of the IR and Raman spectra of Cr(CO)₅(CNCN), which was formed in large excess, reveals that the coordinating CN group of CNCN has coordinating and vibrational properties almost identical to those of the CO ligands in this complex.     

Photochemical reactions of metal carbonyls [M(CO)6 (M = Cr,Mo and W), Re(CO)5Br,Mn(CO)3Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh)

Five new complexes, [M(CO)₅(apmsh)] [M = Cr; (1), Mo; (2), W; (3)], [Re(CO)₄Br(apmsh)] (4) and [Mn(CO)₃(apmsh)] (5) have been synthesized by the photochemical reaction of metal carbonyls [M(CO)₆] (M = Cr, Mo and W), [Re(CO)₅Br], and [Mn(CO)₃Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh). The complexes have been characterized by elemental analysis, mass spectrometry, f.t.-i.r. and ¹H spectroscopy. Spectroscopic studies show that apmsh behaves as a monodentate ligand coordinating via the imine N donor atom in [M(CO)₅(apmsh)] (1–4) and as a tridentate ligand in (5).     

Komplexchemie P-reicher Phosphane und Silylphosphane. VII. Carbonylkomplexe des Heptaphosphans(3) iPr2(Me3Si)P7

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII Carbonyl Complexes of the Heptaphosphane(3) iPr₂(Me₃Si)P₇ From the reaction of iPr₂(Me₃Si)P₇ 1 with one equivalent of Cr(CO)₅THF the yellow products iPr₂(H)P₇[Cr(CO)₅] 2 and iPr₂(Me₃Si)P₇[Cr(CO)₅] 3 were isolated by column chromatography on silicagel. The P? H group in 2 results from a cleavage of the P? SiMe₃ bond during chromatography. The Cr(CO)₅ group in 2 is linked to an iPr? P^e atom, in 3 to the Me₃Si? P^e atom of the P₇ skeleton. The substituents do not force the formation of a single isomer; nevertheless 3 ist considerably favoured as compared to 2 . From the reaction of 1 with 2 equivalents of Cr(CO)₅THF the yellow iPr₂(H)P₇[Cr(CO)₅]₂ 4 was isolated bearing one Cr(CO)₅ group at an iPr? P^e atom, the other one at a P^b atom of the P₇ skeleton. Compound 3 yields with Cr(CO)₄NBD the red iPr₂(Me₃Si)P₇[Cr(CO)₅][Cr(CO)₄] 5 . Three isomers of 5 appear. Two P^e atoms of 5 are bridged by the Cr(CO)₄ group, the third P^e atom is linked to the Cr(CO)₅ ligand. iPr₂(H)P₇[Fe(CO)₄] was isolated from the reaction of 1 with Fe₂(CO)₉. ³¹P NMR and MS data are reported.     

Investigation of the formation of new bimetallic clusters of the type (η-C5Me5)2M2M′2(μ3-S)4(CO)2 (M  Cr,Mo; M′  Co), containing the M2M′2S4 core

The reaction of the sulfur rich pentamethylcyclopentadiene complexes (C₅Me₅)₂Cr₂S₅ and (C₅Me₅)₂Mo₂S₄ with Co₂(CO)₈ results in the formation of new bimetallic clusters of composition (C₅Me₅)₂M₂Co₂(μ₃-S)₄(CO)₂ (M  Cr, Mo), containing the M₂Co₂S₄ core.     

Reaktionen an komplexgebundenen liganden: XXXVI. Synthese und oxidationsverhalten von M(CO)5-komplexen (M = Cr,Mo, W) mit amin- und benzochinondiimin-liganden

The oxidation of yellow Cr(CO)₅NH₂R complexes (NH₂R = aniline, m-toluidine, 3,5-xylidine, m-anisidine) with Pbac₄ gives deep blue to deep purple coloured compounds, which have been identified as the respective [Cr(CO)₅(N-phenyl-1,4-benzochinon-diimine)] complexes. Oxidation of the p-phenylenediamine complex yields [(OC)₅CrHNC₆H₄NHCr(CO)₅], which is also deep blue. The binuclear blue complex [{Cr(CO)₅}₂HNC₆H₄NC₆H₅] is obtained by treating Cr(CO)₅THF with the free ligand in THF/hexane; it dissociates rapidly in acetone to form [Cr(CO)₅HNC₆H₄NC₆H₅] and Cr(CO)₅. Analogous Mo(CO)₅ and W(CO)₅ complexes could not be obtained. The oxidation of [W(CO)₅(m-anisidine)] by I₂ yields [W(CO)₄I]₂. All the compounds were characterized by spectroscopic methods as well as by elemental analysis.     

Darstellung und spektroskopische Charakterisierung von Bindungsisomeren Halogenoselenocyanatoosmaten(IV)

Preparation and Spectroscopic Characterization of Bondisomeric Halogenoselenocyanatoosmates (IV) The new compounds [OsCl₅(NCSe)]^2?, [OsCl₅(SeCN)]^2?, tr.-[OsCl₄(NCSe)(SeCN)]^2?, tr.-[OsCl₄I(NCSe)]^2? and tr.-[OsCl₄I(SeCN)]^2? are prepared from [OsCl₅I]^2? and tr.-[OsCl₄I₂]^2? by oxidative ligand exchange with (SeCN)₂ or by reaction with suspended Pb(SeCN)₂ in CH₂Cl₂ and isolated by ion exchange chromatography on DEAE cellulose. The bondisomers are significantly distinguished by the frequencies of innerligand vibrations: ν_CN(Se), ν_CN(N), ν_CSe(N) > ν_CSe(Se), δ_NCSe >, δ_SeCN. The electronic spectra measured at 10 K on the solid salts exhibit in the region 450–650 nm intensive Se → Os and N → Os charge transfer bands. Essentially weaker intraconfigurational transitions (t) are observed near to 2000 and 1000 nm, splitted by lowered symmetry (C_4v) and spin orbit coupling. Only some of the 0–0-transitions may be assigned by measuring electronic Raman bands with the same frequencies.     

Basische metalle : IX. Synthese und kristallstruktur von C5H5Co(PMe3)CS2. Reaktionen zu zweikernkomplexen mit Co(SCS)Cr- und Co(SCS)Mn-Brückenbindungen

C₅H₅Co(PMe₃)CS₂ (IV) is formed in practically quantitative yield in the reaction of C₅H₅Co(PMe₃)₂ (I) or the heterobinuclear complex C₅H₅(PMe₃)Co(CO)₂Mn(CO)C₅H₄Me (III) with CS₂. The crystal structure shows that the carbon disulfide bonds as a dihapto ligand through the carbon and one sulfur atom (S(2)) (CoC = 1.89, CoS(2) = 2.24 Å, S(2)CS(1) = 141.2°). The two CS bond lengths in IV (CS(2) = 1.68, CS(1) =1.60 Å) are greater than in free CS₂ (1.554Å) which is in agreement with the strong π-acceptor character of h²-CS₂ as shown in the spectroscopic data. IV reacts with Cr(CO)₅THF and C₅H₅Mn(CO)₂THF to give the complexes C₅H₅(PMe₃)Co(SCS)Cr(CO)₅ (V) and C₅H₅(PMe₃)Co(SCS)Mn(CO)₂C₅H₅ (VI) respectively, in which the sulfur atom S(1) that is not bound to cobalt coordinates to the 16-electron fragments Cr(CO)₅ and Mn(CO)₂C₅H₅. The spectroscopic data of IV, V and VI are discussed.     

Synthese und Struktur der Phosphor-verbrückten Übergangsmetallkomplexe [Fe2(CO)6(PR)6] (R = tBu,iPr), [Fe2(CO)4(PiPr)6], [Fe2(CO)3Cl2(PtBu)5], [Co4(CO)10(PiPr)3], [Ni5(CO)10(PiPr)6] und [Ir4(C8H12)4Cl2(PPh)4]

Synthesis and Structure of the Phosphorus-bridged Transition Metal Complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu, ⁱPr), [Fe₂(CO)₄(PⁱPr)₆], [Fe₂(CO)₃Cl₂(P^tBu)₅], [Co₄(CO)₁₀(PⁱPr)₃], [Ni₅(CO)₁₀(PⁱPr)₆], and [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] (P^tBu)₃ and (PⁱPr)₃ react with [Fe₂(CO)₉] to form the dinuclear complexes [Fe₂(CO)₆(PR)₆] (R = ^tBu: 1 ; ⁱPr: 2 ). 2 is also formed besides [Fe₂(CO)₄(PⁱPr)₆] ( 3 ) in the reaction of [Fe(CO)₅] with (PⁱPr)₃. When PⁱPr(P^tBu)₂ and PⁱPrCl₂ are allowed to react with [Fe₂(CO)₉] it is possible to isolate [Fe₂(CO)₃Cl₂(P^tBu)₅] ( 4 ). The reactions of (PⁱPr)₃ with [Co₂(CO)₈] and [Ni(CO)₄] lead to the tetra- and pentanuclear clusters [Co₄(CO)₁₀(PⁱPr)₃] ( 5 ), [Ni₄(CO)₁₀(PⁱPr)₆] [2] and [Ni₅(CO)₁₀(PⁱPr)₆] ( 6 ). Finally the reaction of [Ir(C₈H₁₂)Cl]₂ with K₂(PPh)₄ leads to the complex [Ir₄(C₈H₁₂)₄Cl₂(PPh)₄] ( 7 ). The structures of 1–7 were obtained by X-ray single crystal structure analysis (1: space group P2₁/c (Nr. 14), Z = 8, a = 1 758.8(16) pm, b = 3 625.6(18) pm, c = 1 202.7(7) pm, β = 90.07(3)°; 2 : space group P1 (Nr. 2), Z = 1, a = 880.0(2) pm, b = 932.3(3) pm, c = 1 073.7(2) pm, α = 79.07(2)°, β = 86.93(2)°, γ = 72.23(2)°; 3 : space group Pbca (Nr. 61), Z = 8, a = 952.6(8) pm, b = 1 787.6(12) pm, c = 3 697.2(30) pm; 4 : space group P2₁/n (Nr. 14), Z = 4, a = 968.0(4) pm, b = 3 362.5(15) pm, c = 1 051.6(3) pm, β = 109.71(2)°; 5 : space group P2₁/n (Nr. 14), Z = 4, a = 1 040.7(5) pm, b = 1 686.0(5) pm, c = 1 567.7(9) pm, β = 93.88(4)°; 6 : space group Pbca (Nr. 61), Z = 8, a = 1 904.1(8) pm, b = 1 959.9(8) pm, c = 2 309.7(9) pm. 7 : space group P1 (Nr. 2), Z = 2, a = 1 374.4(7) pm, b = 1 476.0(8) pm, c = 1 653.2(9) pm, α = 83.87(4)°, β = 88.76(4)°, γ = 88.28(4)°).     

Kristall- und molekülstruktur vonzwei metallcarbonyl-derivaten des PH3: (CO)3Cr(PH3)3 und (CO)5Cr(PH3)

The structures of two carbonylphosphine complexes of chromium were determined by X-ray analysis. cis-Tricarbonyltriphosphinechromium(0), [(CO)₃(PH₃)₃Cr], crystallizes in space group P2₁/m with a = 6.90± 0.01, b = 11.29±0.02, c = 6.41±0.01 Å, β = 93.80±0.08°, Z=2. The structure was solved by conventional methods and refined by least squares (R₁ = 0.056). The idealized octahedral molecule shows approximate C_3v, symmetry. The mean CrP-distance is 2.346±40.003 Å. Pentacarbonylphosphinechromium, [(CO)₅(PH₃)Cr], crystallizes in spacegroup Pnma with a = 12.23±0.02, b = 11.33±0.02, c = 6.61 ±0.01 Å, Z = 4. Cell dimensions and structural parameters are very similar to those of hexacarbonylchromium(0). In the crystal the PH₃ group is disordered over three mutually cis-positions of the coordination octahedron.     

Komplexe mit Antimon‐Liganden: [tBu2(Cl)SbW(CO)5], [tBu2(OH)SbW(CO)5], O[SbPh2W(CO)5]2, E[SbMe2W(CO)5]2 (E = Se,Te), cis‐[(Me2SbSeSbMe2)2Cr(CO)4]

Complexes Containing Antimony Ligands: [^tBu₂(Cl)SbW(CO)₅], [^tBu₂(OH)SbW(CO)₅], O[SbPh₂W(CO)₅]₂, E[SbMe₂W(CO)₅]₂ (E = Se, Te), cis‐[(Me₂SbSeSbMe₂)₂Cr(CO)₄] Syntheses of [^tBu₂(Cl)SbW(CO)₅] ( 1 ), [^tBu₂(OH)SbW(CO)₅] ( 2 ), O[SbPh₂W(CO)₅]₂ ( 3 ), Se[SbMe₂W(CO)₅]₂ ( 4 ), cis‐[(Me₂SbSeSbMe₂)₂Cr(CO)₄] ( 5 ) Te[SbMe₂W(CO)₅]₂ ( 6 ) and crystal structures of 1 – 5 are reported.     

Photochemically induced reactions of decacarbonyldimanganese(0)

Photolysis at ca. 350 nm of Mn₂(CO)₁₀ in the presence of each of I₂, CH₃I, SnI₄, CuCl₂ - 2 H₂O, HgX₂ (X  Cl, Br or I), C₆H₅HgI, η⁵-C₅H₅Cr(NO)₂Cl, (η⁵-C₅H₅)₂Cr₂(NO)₄ and [Co₂(CNCH₃)₁₀](BF₄)₄, generally under N₂ or CO in several organic solvents (mainly cyclohexane and THF), was investigated. The observed photoreactions are best rationalized in terms of initial homolytic cleavage of the MnMn bond. In the presence of a halogen (X)-containing compound, the resultant Mn(CO)₅· radical abstracts X to yield Mn(CO)₅X. These reactions are characterized by high quantum efficiencies (generally, _φ-Mn2(CO)10?0.36). Following the abstraction, the remaining metal-containing species (usually a radical), SnCl₃·, CuCl, HgX·, C₆H₅Hg· or η⁵-C₅H₅Cr(NO)₂·, undergoes further abstraction of halogen by Mn(CO)₅·, coupling with the Mn(CO)₅· or ligand substitution. Isolated metal-containing products include SnI₂, Cu, Mn(CO)₅HgX, Hg, [Mn(CO)₅]₂Hg and η⁵-C₅H₅Cr(CO)₂NO. Photolysis of Mn₂(CO)₁₀ in the presence of each of the metal-metal bonded compounds, (η⁵-C₅H₅)₂Cr₂(NO)₄ and [Co₂(CNCH₃)₁₀](BF₄)₄, does not give the respective heterodinuclear combinations, (η⁵-C₅H₅)(NO)₂CrMn(CO)₅ and [(CH₃NC)₅CoMn(CO)₅]²⁺, as detectable or isolable species; instead, η⁵-C₅H₅Cr(CO)₂NO, Mn(CO)₄NO, Mn₂(CO)₉CNCH₃, and [Mn(CO)(CNCH₃)₅]₊ are among the isolated products. The photoreaction between Mn₂(CO)₁₀ and CH₃I provides a convenient synthesis of Mn(CO)₅I.     

Complex formation between benzene and [Cr(CO)3(η6-arene)]

1/1 complex formation between benzene-d₆ and [Cr(CO)₃(η⁶-arene)] (arene = C₆H₅R (R = H, Me, OMe, Cl), C₁₀H₈) has been observed by PMR spectroscopy. The equilibrium constant in the case of arene =C₆H₆ confirms earlier chemical evidence that the [Cr(CO)₃] unit exerts an electron-with-drawing effect upon aromatic rings which is approximately equal to that of the nitro group.     

Chemie polyfunktioneller Moleküle. 97. Beiträge zur Komplexchemie des Lithium-bis(diphenylphosphino)amids,des Bis(diphenylphosphino)amins und des Tris(diphenylphosphino)amins

Chemistry of Polyfunctional Molecules. 97. Contributions to the Coordination Chemistry of Lithium-bis(diphenylphosphino)amide, Bis(diphenylphosphino)amine, and Tris(diphenyl-phosphino)amine (Ph₂P)₂NLi ( 1 ) forms with AuCl(PPh₃) the already known complex [Au(Ph₂P)₂N]₂ ( 2 ), which now has been proved by mass spectroscopy to possess the postulated dimeric structure. 2 gives with HCl, HClO₄, and HBF₄ the new compounds [ClAu(Ph₂P)₂NH]₂ ( 3a ) and [Au(Ph₂P)₂NH…?X]₂ [X = ClO₄ ( 3b ), BF₄ ( 3c )]. In analogy the neutral complex Fe(C₅H₅)(CO)(Ph₂P)₂N ( 5 ) os obtained from FeCl(C₅H₅)(CO)₂ and 1. 5 reacts with HCl to [Fe(C₅H₅)(CO)(Ph₂P)₂NH…?Cl] ( 6a ). The last one can also be prepared by direct reaction of FeCl(C₅H₅)(CO)₂ with (Ph₂P)₂NH ( 4 ). In the same way FeBr(C₅H₅)(CO)₂ reacts with 4 yielding [Fe(C₅H₅)(CO)(Ph₂P)₂NH…?Br] ( 6b ), which leads under metathesis with NH₄PF₆ to [Fe(C₅H₅)(CO)(Ph₂P)₂NH]PF₆ ( 6c ). With PdCl₂(NCPh)₂ the ligand 1 forms Pd[(Ph₂P)₂N]₂ ( 7 ), which also can be synthesized in another way, but is now for the first time characterized in a spectroscopically detailed manner. Cr(CO)₄(Ph₂P)₂NPPh₂ reacts with AuCl(CO) to Cr(CO)₄(Ph₂P)₂NPPh₂AuCl ( 8 ). This compound gives with Cr(CO)₄(Ph₂P)₂NLi the trimetallic complex (OC)₄Cr(Ph₂P)₂NPPh₂AuN(PPh₂)₂Cr(CO)₄ ( 9 ). (Ph₂P)₃N ( 10 ) yields with AuCl(CO) in the molar ratio of 1:3 the compound [ClAuPh₂P]₃N ( 11 ).