Synthesis and spectroscopic studies of nickel(II) chalcogenolates derived from 1,2-diarylchalcogenolato-o-xylene

Nickel(II) chalcogenolate complexes [Ni(L-L)₂(dppe) Cl₂] (1, 2) have been prepared in high yields by reacting 1,2-diarylchalcogenolato-o-xylene, o-C₆H₄(CH₂EAr)₂ (E = Se or Te; Ar = Ph, C₆H₄OMe-4 and C₆H₄OEt-4), generated in situ, with Ni(dppe)Cl₂ [dppe = 1,2-bis(diphenylphosphino)ethane] in benzene. The structures were established by elemental analyses, molar conductance, i.r. and Raman, electronic ¹H- and ³¹P-n.m.r. and mass spectral data. The analytical and spectroscopic data are consistent with an octahedral geometry around nickel in (1) and (2). The ³¹P-n.m.r. spectra indicate their cis configuration in solution. This revised version was published online in June 2006 with corrections to the Cover Date.     

Studies of the reactions of platinum halo complexes with tin(II) halides

The reaction of a dichloromethane solution of a mixture of cis,trans-[PtCl₂(SMe₂)₂] with a tetrahydrofuran solution of SnBr₂ resulted in oxidation of platinum(II) with halogen exchange producing cis,trans-[PtBr₄(SMe₂)₂]. Reaction of a mixture of cis,trans-[PtCl₂(SEt₂)₂], potassium tetrachloroplatinate(II) or potassium hexachloroplatinate(IV) with SnBr₂ in hydrochloric acid solution resulted in formation of predominantly anionic five-coordinate trichlorostannyl platinum(II) complexes. Reaction of potassium tetrabromoplatinate(II) with SnCl₂ in hydrobromic acid in the presence of tetraphenylphosphonium bromide affords cis-[PPh₄]₂[PtBr₂(SnBr₃)₂]. The insertion of SnCl₂ into Pt–Cl bond of platinum(II) complexes cis-[PtCl₂(L₂)] {L₂ = (PPh₃)₂; (PMe₃)₂; {P(OMe)₃}₂; dppm (bis(diphenylphosphino)methane); dppa (bis(diphenylphosphino)amine); and dppe (1,2-bis(diphenylphosphino)ethane)} is described.     

Copper(II), nickel(II) and zinc(II) complexes ofN,N′, N″, N‴-tetra(2-cyanoethyl)-1,4,8, 12-tetra-azacyclopentadecane

Summary Reaction of 1,4,8, 12-tetra-azacyclopentadecance ([15])-aneN₄) with an excess of acrylonitrile gives theN-tetracyanoethylated ligand (L). Several new complexes of this ligand with nickel(II), copper(II) and zinc(II) have been prepared and characterised. The complexes can be formulated [NiL]_n(ClO₄)_2n, [ML](ClO₄)₂ (M=Cu^II and Zn^II), [NiL(NCS)₂], [NiLCl₂], [CuL](NO₃)₂ and [NiL]_n(NO₃)_2n·2H₂O. Spectral, magnetic and conductivity data are reported and possible structures are considered.     

Nickel(II) and cobalt(II) coordination compounds of dichloroguanidinopyrimidines

Summary New coordination compounds of Ni^II and Co^II with dichloropyrimidinoguanidine (L) have been obtained and characterized by physico-chemical and spectroscopic methods. The complexes have the general formulae: [ML₃](ClO₄)₂, [ML₂(SO₄)], [ML₂(NCS)₂], (M = Ni or Co), [NiL₂(ClO₄)₂] and [CoL₂](ClO₄)₂. The ligands are bonded to the metal ion via one nitrogen atom from the pyrimidine heterocyclic ring and one from the guanidine group.     

Syntheses and characterization of cobalt(II) and iron(III) complexes with the Schiff basesN-(o-hydroxybenzylidene)-2-aminobenzimidazole andN-(o-hydroxybenzylidene)-2(2′-aminophenyl)benzimidazole

Summary N-(o-hydroxybenzylidene)-2-aminobenzimidazole (HL) andN-(o-hydroxybenzylidene)-2(2-aminophenyl)benzimidazole (HL) react with CoX₂ (X=Cl, Br, or NCS) and FeCl₃ yielding complexes of general formulae [Co(HL)₂X₂], [Co(HL)₂X₂], [FeCl₂(HL)₂] [FeCl₄], and [FeCl₂(HL)₂][FeCl₄]. Moreover, it was possible to isolate the complexes [Co(HL)Br₂] [Co(L)Cl] and [Co(L)Cl]. The complexes were characterized by elemental analyses, i.r. and electronic spectroscopies and conductivity and magnetic measurements at different temperatures.     

Ruthenium(II) ligated to tetradentate diaminodithioethers: synthesis,characterisation and electrochemistry

Ruthenium(II) complexes containing two tetradentate ligands, 1,2-bis(o-aminophenylthio)ethane (L¹) and 1,2-(oaminophenylthio)xylene (L²), have been prepared. The complexes, which are of the type Ru(L)Cl₂ [L = L¹ (1);/L² (2)], [Ru(L)(PPh₃)Cl]Cl [L = L¹ (3); L² (4)] and [Ru(L)(bpy)](PF₆)₂ [L = L¹ (5);/L² (6)], were characterised by elemental analysis, i.r., u.v.-vis. and n.m.r. spectroscopy and their electrochemical behaviour has been examined by cyclic voltammetry using a glassy carbon working electrode and an Ag/AgCl electrode as the reference electrode. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthetic and spectroscopic characterization of Rh(I)-( S )-amino acid complexes with diphosphine and triphosphine ligands

Reaction of [Rh(η⁴-cod)(S)-amino-acidato] ((S)-amino acidate?=?(S)-O₂C-CHR-NH₂; cod?=?cycloocta-1,5-diene) with 1,2-bis(diphenylphosphino)ethane (dppe) affords the ionic [Rh(dppe)₂]{(S)-O₂C-CHR-NH₂} (R?=?Me, I; Ph, II) complexes. Reactions with 1,3-bis(diphenylphosphino)propane (dppp) or 2,2,2-tris(diphenylphosphinomethyl)ethane (triphos) give the neutral [Rh(dppp){(S)-O₂C-CHR-NH₂}] (R?=?Me, III; Ph, IV) or [Rh(η²-triphos){(S)-O₂C-CHR-NH₂}] (R?=?Me, V; Ph, VI) complexes. The complexes are characterized by elemental analysis, UV–Vis-, IR-, ¹H/³¹P{¹H} NMR- and mass-spectroscopy. Two molecules of dppe coordinate to the Rh(I) symmetrically by replacing both cod and (S)-amino acidate to give I–II. Only one molecule of dppp (or triphos) coordinate to the Rh(I) asymmetrically by replacing only cod to give III–VI. Two diastereomeric Rh(I)-complexes are present in V and VI. The results further suggest that the ligands are arranged in a distorted square planar geometry around the Rh(I) centre. The use of triphos instead of dppe or dppp yields the same coordination sphere.     

Indenyl complexes of ruthenium containing thiolate ligands. Structure of IndRu(dppe)SPh

The indenyl ruthenium thiolate complexes IndRu(PPh₃)₂SR, (1) [Ind = η⁵-C₉H₇; R = Pr ⁿ (a), Ph (b), CH₂Ph(c)] were prepared directly by reacting the thiolate anions (RS⁻) with IndRu(PPh₃)₂Cl. The one-pot reaction of IndRu(PPh₃)₂Cl, thiolate anions and dppa ligands gave IndRu(dppa)SR [dppa= bis(diphenylphosphino)ethane: dppe (2); bis(diphenylphosphino)methane: dppm (3)]. Complexes (1) readily react with NOBF₄ in THF at room temperature to give [IndRu(PPh₃)(NO)SR]BF₄, (4). Complexes (1)–(4) have been characterized by spectroscopic techniques (i.r.,¹H-n.m.r., ³¹P-n.m.r.) and by elemental analysis. The crystal structure of IndRu(dppe)SC₆H₅, (2b) has been determined by X-ray analysis.     

Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2]

The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].     

Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2]

The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].     

Chemistry of Ruthenium Polypyridine Complexes: V. Electronic Structure of Ruthenium(II) Bipyridine-Diphosphine Mixed-Ligand Complexes

Comparative analysis of the donor-acceptor capacities of diphosphine ligands in two series of complexes: cis-[Ru(bpy)2(LL)]^{q +} [LL = 2,2'-bipyridine (bpy), o-benzoquinonediimine (bqdi), cis-1,2-bis(diphenylphosphino)ethane, cis-1,2-bis(diphenylphosphino)ethylene (dppen), (NH3)2, and (CO)2] and [Ru(NH₃)₄. (LL)]^{2 +} (LL = bpy, dppen, and bqdi), was performed. Diphosphines are the strongest donors; they compare in -acceptor capacity which is associated with phosphorus d orbitals with 2,2'-bipyridine and fall far short of o-benzoquinonediimine and carbonyl.     

Symmetric Ni(II) dithiocarbamates with bidentate phosphines ligands

Ni(II) mononuclear dithiocarbamate complexes with bidentate P,P ligands of composition [Ni(R₂dtc)(P,P)]X {R?=?pentyl (pe), benzyl (bz); dtc?=?S₂CN^?; P,P?=?1,2-bis(diphenylphosphino)ethane (dppe), 1,4-bis(diphenylphosphino)butane (dppb), 1,1′-bis(diphenylphosphino) ferrocene (dppf); X?=?ClO₄, Cl, Br, NCS} and binuclear complexes of composition [Ni₂(μ-dpph)(R₂dtc)₂]X₂ with a P,P-bridging ligand {P,P?=?1,6-bis(diphenylphosphino)hexane (dpph); X?=?Cl, Br, NCS} have been synthesized. The complexes have been characterized by elemental and thermal analysis, IR, electronic and ³¹P{¹H}-NMR spectroscopy, magnetochemical and conductivity measurements. Single crystal X-ray analysis of [Ni(pe₂dtc)(dppf)]ClO₄ confirmed a distorted square planar coordination in the NiS₂P₂ chromophore. For selected samples, the catalysis of graphite oxidation was studied.     

Ruthenium(II) complexes with ferrocene-modified arene ligands: synthesis and electrochemistry

A series of arene-ruthenium complexes of the general formula [RuCl₂{η⁶-C₆H₅(CH₂)₂R}L] with R=OH, CH₂OH, OC(O)Fc, CH₂OC(O)Fc (Fc=ferrocenyl) and L=PPh₃, (diphenylphosphino)ferrocene, or bridging 1,1^′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl₃ · nH₂O to afford [RuCl₂{η⁶-C₆H₅(CH₂)₂OC(O)Fc}]₂, and (b) esterification between ferrocene carboxylic acid and [RuCl₂{η⁶-C₆H₅(CH₂)₃OH}L] to give [RuCl₂{η⁶-C₆H₅(CH₂)₃OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl₂{η⁶-C₆H₅(CH₂)₃OH}(PPh₃)] shows that the presence of a CH₂CH₂CH₂OH side-arm allows [RuCl₂{η⁶-C₆H₅(CH₂)₃OH}(PPh₃)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.     

Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide

Reactions of SnCl₂ with the complexes cis‐[PtCl₂(P₂)] (P₂=dppf (1,1′‐bis(diphenylphosphino)ferrocene), dppp (1,3‐bis(diphenylphosphino)propane=1,1′‐(propane‐1,3‐diyl)bis[1,1‐diphenylphosphine]), dppb (1,4‐bis(diphenylphosphino)butane=1,1′‐(butane‐1,4‐diyl)bis[1,1‐diphenylphosphine]), and dpppe (1,5‐bis(diphenylphosphino)pentane=1,1′‐(pentane‐1,5‐diyl)bis[1,1‐diphenylphosphine])) resulted in the insertion of SnCl₂ into the Pt? Cl bond to afford the cis‐[PtCl(SnCl₃)(P₂)] complexes. However, the reaction of the complexes cis‐[PtCl₂(P₂)] (P₂=dppf, dppm (bis(diphenylphosphino)methane=1,1′‐methylenebis[1,1‐diphenylphosphine]), dppe (1,2‐bis(diphenylphosphino)ethane=1,1′‐(ethane‐1,2‐diyl)bis[1,1‐diphenylphosphine]), dppp, dppb, and dpppe; P=Ph₃P and (MeO)₃P) with SnX₂ (X=Br or I) resulted in the halogen exchange to yield the complexes [PtX₂(P₂)]. In contrast, treatment of cis‐[PtBr₂(dppm)] with SnBr₂ resulted in the insertion of SnBr₂ into the Pt? Br bond to form cis‐[Pt(SnBr₃)₂(dppm)], and this product was in equilibrium with the starting complex cis‐[PtBr₂(dppm)]. Moreover, the reaction of cis‐[PtCl₂(dppb)] with a mixture SnCl₂/SnI₂ in a 2 : 1 mol ratio resulted in the formation of cis‐[PtI₂(dppb)] as a consequence of the selective halogen‐exchange reaction. ³¹P‐NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono‐ and bis(trichlorostannyl)platinum complexes. The effect of the alkane chain length of the ligand and Sn^II halide is described.     

Bis(thio­carbohydrazide)dithio­cyanato­iron(II)

In the title compound, [Fe^II(NCS)₂(CH₆N₄S)₂], the Fe^II cation is surrounded by two S atoms and two N atoms from thio­carbohydrazide groups and by two N atoms from thio­cyanate groups. The geometry around the Fe^II cation, which is located on a center of inversion, is distorted octa­hedral. The thio­carbohydrazide mol­ecule assumes a cis–trans conformation, which is reinforced by an N—H⋯N hydrogen bond. Mol­ecules of the title compound are connected via inter­molecular N—H⋯S and N—H⋯N hydrogen bonds to form a three‐dimensional network structure.     

Coordination of di- and triimine ligands at ruthenium(II) and ruthenium(III) centers: structural,electrochemical and radical scavenging studies

Herein, we explore the coordination of di- and triimine chelators at ruthenium(II) and ruthenium(III) centers. The reactions of 2,6-bis-((4-tetrahydropyranimino)methyl)pyridine (thppy), N¹,N²-bis((3-chromone)methylene)benzene-1,2-diamine (chb), and tris-((1H-pyrrol-2-ylmethylene)ethane)amine (H₃pym) with trans-[Ru^IICl₂(PPh₃)₃] afforded the diamagnetic ruthenium(II) complex cis-[RuCl₂(thppy)(PPh₃)] (1) and the paramagnetic complexes [mer-Ru₂(μ-chb)Cl₆(PPh₃)₂] (2), and [Ru(pym)] (3), respectively. The complexes were characterized by IR, NMR, and UV–vis spectroscopy and molar conductivity measurements. The structures were confirmed by single crystal X-ray diffraction studies. The redox properties of the metal complexes were probed via cyclic- and squarewave voltammetry. Finally, the radical scavenging capabilities of the metal complexes towards the NO and 2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl (DPPH) radicals were investigated     

A charge-separation-type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

The reaction of Na[Co^III(d -ebp)] (d -H₄ebp = N,N′-ethylenebis[d -penicillamine]) with [(Au^ICl)₂(dppe)] (dppe = 1,2-bis[diphenylphosphino]ethane) gave a cationic Au^I₄Co^III₂ hexanuclear complex, [Co^III₂(L^Au4)]²⁺ ([ 1 ]²⁺), where [L^Au4]⁴⁻ is a cyclic tetragold(I) metalloligand with a 32-membered ring, [Au^I₄(dppe)₂(d -ebp)₂]⁴⁻. Complex [ 1 ]²⁺ crystallized with NO₃⁻ to produce a charge-separation (CS)-type ionic solid of [ 1 ](NO₃)₂. In [ 1 ](NO₃)₂, the complex cations are assembled to form cationic supramolecular hexamers of {[ 1 ]²⁺}₆, which are closely packed in a face-centered cubic (fcc) lattice structure. The nitrate anions of [ 1 ](NO₃)₂ were accommodated in hydrophilic and hydrophobic tetrahedral interstices of the fcc structure to form tetrameric and hexameric nitrate clusters of {NO₃⁻}₄ and {NO₃⁻}₆, respectively. An analogous CS-type ionic solid formulated as [Ni^IICo^III(L^Au4)](NO₃) ([ 2 ](NO₃)) was obtained when a 1:1 mixture of Na[Co^III(d -ebp)] and [Ni^II(d -H₂ebp)] was reacted with [(Au^ICl)₂(dppe)], accompanied by the conversion of the diamagnetic, square-planar [Ni^II(d -H₂ebp)] to the paramagnetic, octahedral [Ni^II(d -ebp)]²⁻. While the overall fcc structure in [ 2 ](NO₃) was similar to that of [ 1 ](NO₃)₂, none of the nitrate anions were accommodated in any hydrophobic tetrahedral interstice, reflecting the difference in the complex charges between [ 1 ]²⁺ and [ 2 ]⁺.     

Eisen(II)—Phosphin-Komplexe Synthese und Kristallstrukturen von [Fe2I4(dppe)2], [Fe2(SR)4(dppe)2], [Fe(SR′)2(dppp)] und [Fe(SR)2(PMePh2)2] (dppe = Ph2P(CH2)2PPh2; dppp = Ph2P(CH2)3PPh2; R = 2,4,6-Me3C6H2; R′ = 2,4-tBuC6H3)

Iron(II) Phosphane Complexes. Synthesis and Crystal Structures of [Fe₂I₄(dppe)₂], [Fe₂(SR)₄(dppe)₂], [Fe(SR′)₂(dppp)] and [Fe(SR)₂(PMePh₂)₂] (dppe = Ph₂P(CH₂)₂PPh₂; dppp = Ph₂P(CH₂)₃PPh₂; R = 2,4,6-Me₃C₆H₂; R′ = 2,4-tBuC₆H₃) The title compounds were isolated and their structures determined by crystallographic methods. [Fe₂I₄(dppe)₂] ( 1 ) and [Fe₂(SR)₄(dppe)₂] ( 2 ) form dimeric complexes with the bidentate phosphane binding to different iron atoms. The resulting ten-membered rings of both compounds exhibit a nearly identical conformation. The central FeS₂P₂ units of the mononuclear complexes [Fe(SR′)₂(dppp)] ( 3 ) and [Fe(SR)₂(PMePh₂)₂] ( 4 ) show like 2 large deviations from ideal C_2v symmetry with bonding angles around the central iron atom ranging from 97.2, 92.5, and 96.5° (angle P? Fe? P in 2, 3 , and 4 , respectively) to 129.0, 129.9, and 133.6° (angle S? Fe? S in 2, 3 , and 4 , respectively).     

New ruthenium(III) complexes containing tetradentate Schiff bases and their antibacterial activity

Ruthenium(III) complexes, [RuX(EPh₃)(LL)] (X = Cl, Br; E = P, As; LL-acactet, dbm-tet, dbm-o-ph), have been synthesised by reacting [RuCl₃(PPh₃)₃], [RuCl₃(AsPh₃)₃], [RuBr₃(AsPh₃)₃] or [RuBr₃(PPh₃)₂(MeOH)] with tetradentate Schiff bases such as bis(acetylacetone)tetramethylenediimine (H₂acactet), bis(dibenzoylmethane)tetramethylenediimine (H₂dbmtet) and bis(dibenzoylmethane)-o-phenylenediimine (H₂dbm-o-ph). All the complexes have been characterised by elemental analysis, i.r., electronic spectra, e.p.r., magnetic moment and cyclic voltammetric data and an octahedral structure has been tentatively proposed. These new complexes have been tested for their antibacterial activities.     

Pentane and tetra­hydro­furan solvates of trans‐di­chloro­bis­[1,2‐ethane­diyl­bis­(di­phenyl­phos­phine)‐P,P′]­molybdenum(II)

trans‐[MoCl₂(dppe)₂] [dppe is 1,2‐ethane­diyl­bis­(di­phenyl­phos­phine), C₂₆H₂₄P₂] was obtained as a side product from the reaction of trans‐[Mo(dppe)₂(N₂)₂] with Cp*GeCl to give the germyl­yne complex trans‐[Cl(dppe)₂Mo[triple‐bond]Ge(η¹‐Cp*)]. The crystal structures of the hemi­pentane (0.5C₅H₁₂) and di­tetra­hydro­furan (2C₄H₈O) solvates of trans‐[MoCl₂(dppe)₂], (IIIa) and (IIIb), respectively, have been determined.