Darstellung,Kristallstruktur und quantenchemische Berechnung von [C(NMe2)3]2[(CO)4FeInCl3]

Preparation, Structure, and Quantum Chemical Calculation of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] The title compound ( 1 ) has been obtained as colorless crystals by reacting InCl₃ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] in THF solution. The crystal structure determination (monoclinic, C2/c) shows the presence of separate ions with one disordered and one non disordered cation. In the dianion the CO groups of the trigonal bipyramidal coordinated iron atom and the Cl atoms of the tetrahedral coordinated indium atom form a staggered conformation with a relatively short In–Fe bond distance of 252 pm. Quantum Chemical DFT calculations of [CO)₄FeInCl₃]^2– show that the Fe–In bond has a strong ionic character and that it should be considered as an adduct of [Fe(CO)₄]^2– and InCl₃.     

Formation of Unusual Complexes from the Reaction of [C(NMe2)3][(CO)4Fe{C(O)NMe2}] with InMe3; Crystal Structures of [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF

The carbamoyl complex [C(NMe₂)₃][(CO)₄Fe{C(O)NMe₂}] ( 1 ) reacts with InMe₃ under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe₂)₃]₃[Fe₂(CO)₆(μ‐CO){μ‐InFe(CO)₄(μ‐O₂CNMe₂)InFe(CO)₄}] ([C N ₃]₃[ 2 ]) and [C(NMe₂)₃]₂[{(CO)₄Fe}₂In(O₂CNMe₂)]·THF ([C N ₃]₂[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]^3? has a Fe₂(CO)₉‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function.     

The Reaction of [C(NMe2)3][(CO)4FeC(O)NMe2] with InX3 (X = Br,I); Isolation and Crystal Structures of Unusual Addition and Oxidation Products

The reaction between the salt like iron carbamoyl complex [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] ( 1 ) and InBr₃ proceeds with formation of an iron indium bond to give the salt [C(NMe₂)₃]₂[(CO)₄FeInBr₃] ( 2 ). InI₃, however, acts as an oxidation agent to produce with 1 the intercalation compound [FeI₂]₂ · [MeN=C(NMe₂)₂] ( 3 ) as main product. Minor amounts of the penta‐metallic neutral complex [{(CO)₃Fe(μ‐C(NMe₂)O)₂Fe(CO)₂C(NMe₂)O}₂Fe] ( 4 ) and the indium containing salt [C(NMe₂)₃][(CO)₄Fe(μ‐InI₂)₂NMe₂] ( 5 ) were also isolated and characterized by X‐ray analyses.     

Über die Reaktionen von CH2=P(NMe2)3 mit Fe(CO)5, Cr(CO)6 und CS2; Molekülstrukturen von [MeP(NMe2)3][(CO)5CrC(O)CH=P(NMe2)3] und (CO)4Fe=C(OMe)CH=P(NMe2)3

The Reactions of CH₂=P(NMe₂)₃ with Fe(CO)₅, Cr(CO)₆, and CS₂; Molecular Structures of [MeP(NMe₂)₃][(CO)₅CrC(O)CH=P(NMe₂)₃], and (CO)₄Fe=C(OMe)CH=P(NMe₂)₃ The ylide CH₂=P(NMe₂)₃ ( 1 ) reacts with several binary transition metal carbonyls M(CO)_x to produce the corresponding salt like compounds [MeP(NMe₂)₃][(CO)_x–1MC(O)CH=P(NMe₂)₃] (M = Fe ( 3 ), Cr ( 4 )). The related reaction with CS₂ leads to the salt [MeP(NMe₂)₃][SC(S)CH=P(NMe₂)₃] ( 2 ). While 4 is thermally stable, 3 rapidly decomposes at room temperature with formation of [MeP(NMe₂)₃]₂[Fe₂(CO)₈] ( 8 ). Alkylation of 3 (at –50 °C) and 4 with MeSO₃CF₃ produces the related carbene complexes (CO)_x–1M=C(OMe)CH=P(NMe₂)₃ ( 5 ) and ( 6 ); the reaction of 3 with Me₃SiCl results in the formation of the carbene complex (CO)₄Fe=C(OSiMe₃)CH=P(NMe₂)₃ ( 7 ). 4 crystallizes in the space group P2₁2₁2₁ (No. 19) with a = 1111.1(2), b = 1476.1(3), c = 1823.1(4) pm and Z = 4. 5 crystallizes in the space group P2₁/n (No. 14) with a = 1303.6(3), b = 910.5(4), c = 1627.0(4) pm, β = 96.06(2)° and Z = 4. The compounds have been characterized by elemental analyses, NMR (¹H, ¹³C, ³¹P) and IR spectroscopy.     

Über die Reaktion von Cp2TiCl2 mit [C(NMe2)3][(CO)4FeC(O)NMe2] – Kristallstruktur von [C(NMe2)3]2[FeCl4]

Concerning the Reaction of Cp₂TiCl₂ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] – Crystal Structure of [C(NMe₂)₃]₂[FeCl₄] The title compound forms by the reaction of Cp₂TiCl₂ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] in THF solution. It crystallizes in the space group Pbcn with a = 1 566.6(3); b = 976.4(2); c = 1 580.4(4) pm; Z = 4; R = 3.8%. Each [FeCl₄]^2? in is surrounded by eight cations. Two cations each are connected with one Cl atom by relatively short H …? Cl contacts leading to a distortion of the tetrahedral geometry of the anion.     

Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

Syntheses and X‐Ray Structures of μ‐Carbamoyl Complexes of Iron; Isomers of [(CO)3Fe(μ‐Me2NCO)2Fe(CO)2(NHMe2)] with Symmetrical and Asymmetrical Intramolecular NH···O Contacts

Reaction of the carbamoyl complex [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] ( 1 ) with silver salts gives the dinuclear μ‐carbamoyl complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(HNMe₂)] ( 2 ). Depending on the solvent, crystals of 2a with an asymmetrical or of 2b with a symmetrical internal NH···O bridge are formed. The dimethylamino group is originated from a further molecule of 1 from which an amino group is transferred to the “α‐CO” ligand of an intermediate oxidation product while the H⁺ ion probably comes from deprotonation of a guanidinium cation. The HNMe₂ ligand cannot be replaced by CO but easily by PPh₃ to give [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(PPh₃)] ( 3 ). All complexes were studied by X‐ray diffraction analyses and the usual spectroscopic methods.     

Preparation,Spectroscopic Properties,and Crystal Structures of Fe2(CO)6(μ‐CO)(μ‐CF2)2, Fe2(CO)6(μ‐CO)2(μ‐CF2), and Fe2(CO)6(μ‐CF2)(PPh3)2 – Theoretical Studies of Methylenic vs. Carbonyl Bridges in Diiron Complexes

The reaction of Na₂[Fe(CO)₄] with Br₂CF₂ in n‐pentane generates a mixture of the compounds (CO)₃Fe(μ‐CO)_3–n(μ‐CF₂)_nFe(CO)₃ ( 2 , n = 2; 3 , n = 1) in low yields with 3 as the main product. 3 is obtained free from 2 by reacting Br₂CF₂ with Na₂[Fe₂(CO)₈]. The non‐isolable monomeric complex (CO)₄Fe=CF₂ ( 1 ) can probably considered as the precursor for 2 . 3 reacts with PPh₃ with replacement of two CO ligands to form Fe₂(CO)₆(μ‐CF₂)(PPh₃)₂ ( 4 ). The complexes 2 – 4 were characterized by single crystal X‐ray diffraction. While the structure of 2 is strictly similar to that of Fe₂(CO)₉, the structure of 3 can better be described as a resulting from superposition of the two enantiomers 3 a and 3 b with two semibridging CO groups. Quantum chemical DFT calculations for the series (CO)₃Fe(μCO)_3–n(μ‐CF₂)_nFe(CO)₃ (n = 0, 1, 2, 3) as well as for the corresponding (μ‐CH₂) derivatives indicate that the progressively larger σ donor and π acceptor properties for the bridging ligands, in the order CO < CF₂ < CH₂, favor a stronger Fe–Fe bond.     

Koordinativ ungesättigte Dieisenkomplexe: Synthese und Kristallstrukturen von [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]

Coordinatively Unsaturated Diiron Complexes: Synthesis and Crystal Structures of [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] and [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] [Fe₂(μ‐CO)(CO)₆(μ‐H)(μ‐P^tBu₂)] ( 1 ) reacts spontaneously with dppm (dppm = Ph₂PCH₂PPh₂) to give [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 2 c ). By thermolysis or photolysis, 2 c loses very easily one carbonyl ligand and yields the corresponding electronically and coordinatively unsaturated complex [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). 3 exhibits a Fe–Fe double bond which could be confirmed by the addition of methylene to the corresponding dimetallacyclopropane [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ). The reaction of 1 with dppe (Ph₂PC₂H₄PPh₂) affords [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppe)] ( 5 ). In contrast to the thermolysis of 2 c , yielding 3 , the heating of 5 in toluene leads rapidly to complete decomposition. The reaction of 1 with PPh₃ yields [Fe₂(CO)₆(H)(μ‐P^tBu₂)(PPh₃)] ( 6 a ), while with ^tBu₂PH the compound [Fe₂(μ‐CO)(CO)₅(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 6 b ) is formed. The thermolysis of 6 b affords [Fe₂(CO)₅(μ‐P^tBu₂)₂] and the degradation products [Fe(CO)₃(^tBu₂PH)₂] and [Fe(CO)₄(^tBu₂PH)]. The molecular structures of 3 , 4 and 6 b were determined by X‐ray crystal structure analyses.     

Zur Reaktivität des Ferriophosphaalkens (Z)‐[Cp*(CO)2FeP=C(tBu)NMe2] gegenüber Propiolsäureestern HC≡C‐CO2R (R=Me,Et) und Acetylendicarbonsäureestern RO2C‐C≡C‐CO2R (R=Me,Et, tBu)

On the Reactivity of the Ferriophosphaalkene (Z)‐[Cp*(CO)₂Fe‐P=C(tBu)NMe₂] towards Propiolates HC≡C‐CO₂R (R=Me, Et) and Acetylene Dicarboxylates RO ₂C‐C≡C‐CO₂R (R=Me, Et, tBu) The reaction of equimolar amounts of (Z)‐[Cp*(CO)₂Fe‐P=C(tBu)NMe₂] 3 and methyl‐ and ethyl‐propiolate ( 2a, b ) or of 3 and dialkyl acetylene dicarboxylates 1a (R=Me), 1b (Et), 1c (tBu) afforded the five‐membered metallaheterocycles [Cp*(CO) =C(tBu)NMe₂] ( 4a, b ) and [Cp*(CO) =C(tBu)NMe₂] ( 5a—c ). The molecular structures of 4b and 5a were elucidated by single crystal X‐ray analyses. Moreover, the reactivity of 4b towards ethereal HBF₄ was investigated.     

The Ylide Adduct SOC2(PPh3)2 as Complex Ligand. Reaction with [Mn2(CO)10] and InCl3; Crystal Structures of [(CO)4Mn(SOC2{PPh3}2)2][Mn(CO)5] and (H2C{PPh3}2)[InCl4]2

The betain‐like SOC₂(PPh₃)₂ ( 1a ) reacts with [Mn₂(CO)₁₀] in THF to produce the salt‐like complex [(CO)₄Mn(SOC₂{PPh₃}₂)₂][Mn(CO)₅] ( 2 ). 1a is bonded via the sulfur atoms which are arranged in trans position in the octahedral environment of the manganese atom. With InCl₃ from CH₂Cl₂ solution the addition product [Cl₃In(SOC₂{PPh₃}₂)] ( 3 ) is obtained along with the salt (H₂C{PPh₃}₂)[InCl₄]₂ ( 4 ), which is the result of proton abstraction from the solvent. The crystal structures of 2· 0.5THF and 4· CH₂Cl₂ are reported. The compounds are further characterized by IR and ³¹P NMR spectroscopy.     

[Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthese,Kristallstruktur und Koordinationsisomerie

[Fe₂(μ_sb‐CO)(CO)₃(NO)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)]: Synthesis, X‐ray Crystal Structure and Isomerization Na[Fe₂(μ‐CO)(CO)₆(μ‐P^tBu₂)] ( 1 ) reacts with [NO][BF₄] at —60 °C in THF to the nitrosyl complex [Fe₂(CO)₆(NO)(μ‐P^tBu₂)] ( 2 ). The subsequent reaction of 2 with phosphanes (L) under mild conditions affords the complexes [Fe₂(CO)₅(NO)L(μ‐P^tBu₂)], L = PPh₃, ( 3a ); η‐dppm (dppm = Ph₂PCH₂PPh₂), ( 3b ). In this case the phosphane substitutes one carbonyl ligand at the iron tetracarbonyl fragment in 2 , which was confirmed by the X‐ray crystal structure analysis of 3a . In solution 3b loses one CO ligand very easily to give dppm as bridging ligand on the Fe‐Fe bond. The thus formed compound [Fe₂(CO)₄(NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ) occurs in solution in different solvents and over a wide temperature range as a mixture of the two isomers [Fe₂(μ_sb‐CO)(CO)₃(NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4a ) and [Fe₂(CO)₄(μ‐NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4b ). 4a was unambiguously characterized by single‐crystal X‐ray structure analysis while 4b was confirmed both by NMR investigations in solution as well as by means of DFT calculations. Furthermore, the spontaneous reaction of [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) with NO at —60 °C in toluene yields a complicated mixture of products containing [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 6 ) as main product beside the isomers 4a and 4b occuring in very low yields.     

Die Reaktion von tBu2P‐P=P(Me)tBu2 mit [Fe2(CO)9] und [(η2‐C8H14)2Fe(CO)3]

^tBu₂P‐P=P(Me)^tBu₂ reacts with [Fe₂(CO)₉] to give [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₃}{Fe(CO)₄}] ( 1 ) and [trans‐(^tBu₂MeP)₂Fe(CO)₃]( 2 ). With [(η²‐C₈H₁₄)₂Fe(CO)₃] in addition to [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₂PMe^tBu₂}‐{Fe(CO)₄}] ( 10 ) and 2 also [(μ‐P^tBu₂){μ‐P‐Fe(CO)₃‐PMe^tBu₂}‐{Fe(CO)₃}₂(Fe‐Fe)]( 9 ) is formed. 1 crystallizes in the monoclinic space group P2₁/c with a = 875.0(2), b = 1073.2(2), c = 3162.6(6) pm and β = 94.64(3)?. 2 crystallizes in the monoclinic space group P2₁/c with a = 1643.4(7), b = 1240.29(6), c = 2667.0(5) pm and β = 97.42(2)?. 9 crystallizes in the monoclinic space group P2₁/n with a = 1407.5(5), b = 1649.7(5), c = 1557.9(16) pm and β = 112.87(2)?.     

Reactivity of [Te6Fe8(CO)24]2− and Its Conversion to [Te4Fe5(CO)14]2−

Whereas reaction of [PhCH₂NMe₃]₂|Te₆Fe₈(CO)₂₄] (1) in refluxing CH₂CI₂ forms Fe₂(CO)₆(μ0-) TeCH₂Te), treatment of 1 with Ph₂SnCl ₂ or Mel gave the oxidation product Te₂Fe₃(CO)₉. Oxidation of 1 with [Cu(CH₃CN)₄]BF₄ afforded Te₂Fe₃(CO)₉ in good yield. Cluster 1 was converted to [PhCH₂NMe₃][Te₄Fe₅(CO)₁₄] (2) in MeOH/CH₂Cl₂ solution. Cluster 2 was structurally characterized by single-crystal X-ray diffraction and spectral methods. Complex 2 is composed of two Te₂Fe₂(CO)₆ fragments linked by one Fe(CO)₂ group. 2 crystallizes in the orthorhombic space group Pbcn with a = 13.351 (4) Å, b = 13.417 (4) Å, c = 26.077 (3) Å, V = 4671 (2) Å ₃, Z = 4.     

Neue metallorganisch substituierte Indium–Stickstoff-Verbindungen. Synthese und Kristallstrukturen von [{Cp(CO)3Mo}2InN(SiMe3)2] und [{Cp(CO)3Mo}In{N(SiMe3)2}2]

New Organometallic Indium Nitrogen Compounds. Synthesis and Crystal Structures of [{Cp(CO)₃Mo}₂InN(SiMe₃)₂] and [{Cp(CO)₃Mo}In{N(SiMe₃)₂}₂] The reaction of [{Cp(CO)₃Mo}₂InCl] with LiN · (SiMe₃)₂ leads to the formation of [{Cp(CO)₃Mo}₂InN · (SiMe₃)₂] ( 1 ). 1 is monomeric and it contains an indium atom which is coordinated in a trigonal planar manner by two {Cp(CO)₃Mo} fragments and a N(SiMe₃)₂ group. The corresponding bis-amide [{Cp(CO)₃Mo}In{N(SiMe₃)₂}₂] ( 2 ) is prepared by the reaction of [{Cp(CO)₃Mo}InCl₂] with two equivalents of LiN(SiMe₃)₂. In analogy to 1, 2 is monomeric and it contains an indium atom in a trigonal planar coordination.     

Synthese,Struktur und Reaktivität des Ferrioarsaalkens [(η5‐C5Me5)(CO)2FeAs=C(Ph)NMe2]

Synthesis, Structure, and Reactivity of the Ferrioarsaalkene [(η⁵‐C₅Me₅)(CO)₂FeAs=C(Ph)NMe₂] Reaction of equimolar amounts of the carbenium iodide [Me₂N(Ph)CSMe]I and LiAs(SiMe₃)₂ · 1.5 THF afforded the thermolabile arsaalkene Me₃SiAs = C(Ph)NMe₂ ( 1 ), which in situ was converted into the black crystalline ferrioarsaalkene [(η⁵‐C₅Me₅)(CO)₂FeAs=C(Ph)NMe₂)] ( 2 ) by treatment with [(η⁵‐C₅Me₅)(CO)₂FeCl]. Compound 2 was protonated by ethereal HBF₄ to yield [(η⁵‐C₅Me₅)(CO)₂FeAs(H)C(Ph)NMe₂]BF₄ ( 3 ) and methylated by CF₃SO₃Me to give [(η⁵‐C₅Me₅)(CO)₂FeAs(Me)C(Ph)NMe₂]‐ SO₃CF₃ ( 4 ). [(η⁵‐C₅Me₅)(CO)₂FeAs[M(CO)_n]C(Ph)NMe₂] ( 5 : [M(CO)_n] = [Fe(CO)₄]; 6 : [Cr(CO)₅]) were isolated from the reaction of 2 with [Fe₂(CO)₉] or [{(Z)‐cyclooctene}Cr(CO)₅], respectively. Compounds 2 – 6 were characterized by means of elemental analyses and spectroscopy (IR, ¹H, ¹³C{¹H}‐NMR). The molecular structure of 2 was determined by X‐ray diffraction analysis.     

Pt[In–C(SiMe3)3]4 – eine zu Pt(CO)4 analoge Verbindung mit einem durch vier InR‐Liganden ideal tetraedrisch koordinierten Platinatom

Pt[In–C(SiMe₃)₃]₄ – a Pt(CO)₄ Analogous Compound with a Platinum Atom Tetrahedrally coordinated by Four InR Ligands The reaction of the tetrahedral alkylindium(I) compound In₄[C(SiMe₃)₃]₄ ( 1 ) with bis(cyclooctadiene)platinum(0) afforded the compound Pt[InC(SiMe₃)₃]₄ ( 2 ), which is an analogue of the thermally unstable carbonyl complex Pt(CO)₄ and possesses a platinum atom tetrahedrally coordinated by four InR ligands.     

(PPh4)2[(SN)ReCl3(μ‐N)(μ‐NSN)ReCl3(THF)] – ein Nitrido‐Thionitrosyl‐Dinitridosulfato‐Komplex des Rheniums

(PPh₄)₂[(SN)ReCl₃(μ‐N)(μ‐NSN)ReCl₃(THF)] – a Nitrido‐Thionitrosyl‐Dinitridosulfato‐Complex of Rhenium The title compound has been prepared from PPh₄[Re^VIICl₄(NSCl)₂] with excess N(SiMe₃)₃ in dichloromethane solution to give red‐brown single crystals after recrystallisation from acetonitrile/THF solutions. As a by‐product PPh₄[ReNCl₄] is formed. (PPh₄)₂[(SN)ReCl₃(μ‐N)(μ‐NSN)ReCl₃(THF)] ( 1 ): Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 1024.1(1), b = 2350.2(1), c = 2315.4(2) pm, β = 94.09(1)°, R₁ = 0.0403. In the complex anion of 1 the rhenium atoms are connected by an asymmetric Re≡N–Re bridge as well as by a (NSN)^4–‐bridge to form a planar Re₂N(NSN) six‐membered heterocycle. Both rhenium atoms are coordinated by three chlorine atoms, one of them by a thionitrosyl ligand, the other one by the oxygen atom of a thf molecule.     

Coordination chemistry of organometallic polydentate ligand Reactive chemistry of the tridentate ligand trans‐Fe(Ph2PQu‐P)2‐(CO)3 [PhzPQu=2‐diphenyl‐phosphino‐4‐methylquinoline] and molecular structure of [Fe(CO)3(μ‐Ph2PQu)2HgI]+ [HgI3]

Reaction of a new type of bidentate ligand PhPQu [PhPQu = 2‐diphenylphosphino‐4‐methylquinoline] with Fe(CO)₅ in butanol gave trans‐Fe(FpPQu‐P)(CO)₃ (1). Compound 1, which can act as a neutral tridentate organometallic ligand, was reacted with I B, II B metal compounds and a rhodium complex to give six binuclear complexes with Fe? M bonds, Fe(CO)₃ (μ‐Ph₂PQu)MX_n (2–7) [M= Zn(II), Cd(II), Hg(II), Cu(I), Ag(I), Rh(I)], and an ion‐pair complex [Fe(CO)₃ (μ‐Ph₂PQu)₂HgI][HgI₃]^? (8). The structure of 8 was determined by X‐ray crystallography. Complex 8 crystallizes in the space group P‐1 with a = 1.0758(3), b = 1.6210(4), c=1.7155(4)nm; a=75.60(2), β=71.81(2), γ=81.78(2)° and Z = 2 and its structure was refined to give agreement factors of R=0.050 and R_w = 0.057. The Fe‐Hg bond distance is 0.2536nm.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.