Octacarbonyldicobalt reacts with the ditertiary phosphine and arsine (C₆H₅)₂-ECH₂CH₂E(C₆H₅)₂ (E = P, As) in a direct route to give primarily the non CO-bridged, but ligand-bridged complexes Co₂(CO)₆(C₆H₅)₂ECH₂CH₂E(C₆H₅)₂. From Co₂(CO)₆-(C₆H₅)₂PCH₂CH₂P(C₆H₅)₂ secondarily a CO-bridged isomer has been also isolated. The non-CO-bridged form of Co₂(CO)₆(C₆H₅)₂PCH₂CH₂P(C₆H₅)₂ gives insertion reactions with Hg, SnCl₂ and CsGeCl₃ yielding the probably oligo- or polymeric compounds Hg[Co(CO)₃]₂(C₆H₅)₂PCH₂CH₂P(C₆H₅)₂ and Cl₂M[Co(CO)₃]₂(C₆H₅)₂PCH₂CH₂P(C₆H₅)₂ (M = Sn, Ge). The characteristic IR absorptions of all compounds and some Raman spectra are reported.

The reaction of C₃F₇Fe(CO)₃[P(C₆H₅)₃] I with liquid ammonia yields, dependend on the reaction-time C₃F₇Fe(CO)₂(NH₃)₂I and [C₃F₇Fe(CO)₂(NH₃)₃] I. In the contrary, C₃F₇Fe(CO)₄ I undergoes ammonolysis forming NH₄F, NH₄I, NH₄NCO and CO (NH₂)₂. No stable iron-complex could be obtained.

PPh2-Eliminierung aus dem PP-verknüpften Phosphazen Ph2P-N=PPh2-PPh2=N-PPh2 mit [C5H5Fe(CO)(/x-CO)]2; Kristallstrukturanalyse des Phosphazen-Derivats Chemistry of Polyfunctional Molecules, 127 [1] PPh2 Elimination from the PP Connected Phosphazene Ph2P-N=PPh2-PPh2=N-PPh-, with [C5H5Fe(CO)(^-CO)]2; Crystal Structure of the Phosphazene Derivative Jochen Ellermann3’*, Martin Schütz3, Frank W. Heinemann3, Matthias Moll3, Walter Bauerb 3 Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstraße 1, D-91058 Erlangen b Institut für Organische Chemie der Universität Erlangen-Nürnberg, Henkestraße 42, D-91054 Erlangen

Co-2(CO)(8) reacts with bis(diphenylphosphanyl)amine, HN(PPh2)(2) (Hdppa, 1), in two steps to afford the known compound [Co(CO)(Hdppa-kappa(2)P)(2)][Co(CO)(4)]. 2THF (6a . 2THF). The intermediate [Co(CO)(2)(Hdppa-kappa(2)P).(Hdppa-kappa(2)P)][Co(CO)(4)]. dioxane . n-pentane (5 . dioxane . n-pentane) was isolated for the first time and was characterized by X-ray analysis. The cation 5(+) exhibits a slightly distorted trigonal-bipyramidal geometry. Detailed P-31-NMR investigations (solid-state CP/MAS NMR, TOSS, P-31-COSY, P-31-EXSY) showed that the additional tautomer [Co(CO)(2)(Hdppa-kappa(2)P) (Ph2P-N=P(H)Ph-2-kappa P)(+) (5'(+)) is present in solution. The tautomer equilibrium is slow in the NMR time scale. In contrast to the solid state only tetragonal pyramidal species of 5 are found in solution. At -90 degrees C there is slow exchange between the three diastereomeric species 5a(+)-5c(+). Compound 5 forms [Co(CO).(Hdppa-kappa(2)P)(2)]BPh4. THF (6b . THF) in THF with NaBPh4 under GO-Elimination. A X-ray diffraction investigation shows that the cation 6(+) consists of a slightly distorted trigonal-bipyramidal co-ordination polyeder. However, a distorted tetragonal-pyramidal structure has been found for the cation 7(+) of the related compound [Co(CO)(dppm)(2)][Co(CO)(4)]. 2 THF (7 . 2 THF; dppm = bis(diphenylphosphanyl)methane, Ph2PCH2PPh2). A comparison with the known [8] trigonal-bipyramidal stereoisomer, ascertained for 7(+) of the solvent-free 7, is described. In solutions of 6a . 2 THF and 7 . 2 THF C-13{H-1}- and P-31{H-1}-NMR spectra indicate an exchange of all CO and organophosphane molecules between cobalt(I) cation and cobalt(-I) anion. A concerted mechanism for the exchange process is discussed. CO elimination leads to discontinuance of the cyclic mechanism by forming binuclear substitution products such as the isolated Co-2(CO)(2).(mu-CO)(2)(mu-dppm)(2). 0.8 (3) over bar THF (8 . 0.8 (3) over bar THF), which was characterized by spectroscopy and X-ray analysis. For the dissolved [Co(CO)(2)CH3C(CH2PPh2)(3)][Co(CO)(4)]. 0.8 (3) over bar n-pentane (9a . 0.8 (3) over bar n-pentane) no CO and triphos exchange processes between the cation and the anion are observed. Metathesis of 9a . 0.8 (3) over bar n-pentane with NaBPh4 yields [Co(CO)(2)CH3C(CH2PPh2)(3)]BPh4 (9b) which has been characterized by single-crystal X-ray analysis. The cation shows a small distorted tetragonal-pyramidal structure.

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The suspension of LiN(PPh2)(2) (1) in CH2Cl2 that is acting in the case under discussion not only as a solvent but also as an alkylating agent, results in the formation of [Ph2MeP=N=PMePh2]Cl (2). The metathesis of 2 with NaBPh4 in acetone yields the title compound [Ph2MeP=N=PMePh2]BPh4 (3). The crystal structure of 3 has been determined by X-ray crystal analysis. (C) 1999 Elsevier Science S.A. All rights reserved.

The suspension of LiN(PPh2)2 (1) in CH2Cl2 that is acting in the case under discussion not only as a solvent but also as an alkylating agent, results in the formation of [Ph2MePNPMePh2]Cl (2). The metathesis of 2 with NaBPh4 in acetone yields the title compound [Ph2MePNPMePh2]BPh4 (3). The crystal structure of 3 has been determined by X-ray crystal analysis.

The reaction of Co2(CO)8 and Ph2P-N*PPh2-PPh2*N-PPh2 (1) in a molar ratio between 1:1 and 1:3 in toluene always leads to the formation of both the yellow by-product [fac-Co(CO)3(Ph2P-N*PPh2-PPh2*N-PPh2-P,P′)] [Co(CO)4] (4) and the red compound [(Co)2(μ-CO)(CO)4(μ-Ph2P-N-PPh2)2] (5) that has already been characterized by spectroscopic data and X-ray analysis. Whereas 4 is obtained as a precipitate, the red compound 5 stays in solution and reacts in presence of air with the remaining ligand 1 in a non-stoichiometrical reaction to the violet cobalt(III) complex [Co(η1-O-PPh2*N-PPh2*O)(η2-O-PPh2*N-PPh2*O)2] (6). The crystal structure of 6 proves a distorted trigonal bipyramidal coordination of the oxygen atoms at the Co(III) ion. Surprisingly, complex 6 shows an unusual paramagnetism according to four unpaired electrons (5.21±0.04 BM).

European Journal of Inorganic ChemistryVolume 1998, Issue 4 p. 437-444 Chemistry of Polyfunctional Molecules, 129: Full Paper Synthesis and X-Ray Structures of Novel Lead(1+) and Indium(3+) Phosphazenide Complexes; Detailed 207Pb-NMR Spectra of the 207Pb-Labelled Dimeric Lead(1+) Species Astrid Winkler, Astrid Winkler Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorWalter Bauer, Walter Bauer bauer@organik.uni-erlangen.de Search for more papers by this authorFrank W. Heinemann, Frank W. Heinemann Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorVeronica Garcia-Montalvo, Veronica Garcia-Montalvo Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorMatthias Moll, Matthias Moll Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorJochen Ellermann, Jochen EllermannSearch for more papers by this author Astrid Winkler, Astrid Winkler Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorWalter Bauer, Walter Bauer bauer@organik.uni-erlangen.de Search for more papers by this authorFrank W. Heinemann, Frank W. Heinemann Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorVeronica Garcia-Montalvo, Veronica Garcia-Montalvo Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorMatthias Moll, Matthias Moll Institut für Anorganische Chemie der Universität Erlangen-Nürnberg, Egerlandstrasse 1, D-91058 Erlangen, Fax: (internat.) +49(0)9131/85-7367Search for more papers by this authorJochen Ellermann, Jochen EllermannSearch for more papers by this author First published: April 1998 https://doi.org/10.1002/(SICI)1099-0682(199804)1998:4<437::AID-EJIC437>3.0.CO;2-9Citations: 14AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Abstract The reaction of PbCl2 with LiN(PPh2)2 (1) at −78°C affords the P−P coupled phosphazene Ph2P−N=PPh2−PPh2=N−PPh2 (2) as an oxidation product and, as a reduction equivalent, the novel lead(1+) complex [(Pb1+)2(μ-Ph2P···N···PPh2−)2](Pb−Pb) (3). The crystal structure determination of the red compound 3 shows a Pb−Pb bond length of 304.1(1) pm. The 31P- and 207Pb-NMR spectra of 3 are complicated due to the presence of a higher order spin system (AA′A′′A′′′X for the mono-207Pb isotopomer, AA′A′′A′′′XX′ for the bis-207Pb isotopomer). Simulations of the 31P and 207Pb spectra both on material with natural isotope abundance and on the 207Pb-labelled compound (3*) reveal a large Pb,Pb coupling constant of 7708 Hz, indicative of a covalent Pb−Pb bond. − Though InCl3 is diagonally related to PbCl2, no significant redox process is observed in the reaction between InCl3 and 1. The yellow crystals of [In3+(Ph2P···N···PPh2−)3] (4) that are obtained were also investigated by X-ray analysis. These show a propeller-like configuration of the three four-membered chelate rings with indium(3+) as the centre. Citing Literature Volume1998, Issue4April 1998Pages 437-444 RelatedInformation

The metalation of bis(diphenylphosphanyl)amine, HN(PPh2)2 (5), with RbOtBu in the presence of N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDTA (3)) in toluene surprisingly affords the nearly PMDTA free RbN(PPh2)2 (6a). Recrystallization of 6a from tetrahydrofuran (THF) yields RbN(PPh2)2ċ0.5 THF (6b). Compounds 6a, b crystallize in thin needles; however, these are not suitable for X-ray structure analyses. The reactions of 5 with MOtBu (M=Rb, Cs) in the presence of 18-crown-6 in toluene yield the monomeric, pale yellow rubidium and caesium complexes [Rb(18-crown-6)(N(PPh2)2)] (7) and [Cs(18-crown-6)(N(PPh2)2)] (8), respectively. Allowing to stand a solution of 8 in THF for three months at 20°C results in a cleavage product of 8. This is identified as the dimeric yellow complex [(Cs(18-crown-6))2(μ-N*P(H)Ph2)2]ċTHF (9). The source of the hydrogen atom in the bridging phosphorane iminate anion [N*P(H)Ph2]− is uncertain. Compounds 7–9 are structurally characterized by X-ray analyses. These reveal that [N(PPh2)2]− acts as P-ligating chelate in 7, whereas it coordinates the Cs+ as N-donor as well as η2 C-donor with one phenyl group in 8. No phosphorus coordination is observed in 8. The two caesium cations in 9 are two-fold N-bridged by [N*P(H)Ph2]−. The coordination sphere of each caesium atom is completed by a 18-crown-6 ligand. The solid state 13C NMR spectrum of 8 reveals dynamic phenomena (rotation of the 18-crown-6 ligand). In the solid state 31P spectrum of 8, 31P, 31P–J-coupling is observed between the chemically non-equivalent phosphorus sites (J=390 Hz).

The reaction of Ph 2 P-N=PPh 2 -PPh 2 =N-PPh 2 (Ph = C 6 H 5 , 2) with [CpFe(CO)(μ-CO)] 2 (Cp = C 5 H 5 , 3) yields under elimination of a PPh 2 -group from 2 and cleavage of the Fe-Fe bond in 3 the monocyclic ferraphosphazene complex Cp(OC) (4) and Ph 2 P-PPh 2 (5). In a side reaction the P-P bond of 2 is also cleaved in a redox process to give Cp(OC) (7). Compound 4 has been characterized by a crystal structure determination.

The reaction of Ph2P-N=PPh2-PPh2=N-PPh2 (Ph = C6H5, 2) with [CpFe(CO)(mu-CO)](2) (Cp = C5H5, 3) yields under elimination of a PPh2-group from 2 and cleavage of the Fe-Fe bond in 3 the monocyclic ferraphosphazene complex Cp(OC)Fe-Ph2P-N=PPh2=N-PPh2 (4) and Ph2P-PPh2 (5). In a side reaction the P-P bond of 2 is also cleaved in a redox process to give Cp(OC)Fe-Ph2P-N-PPh2 (7). Compound 4 has been characterized by a crystal structure determination.

AbstractBis(diphenylphosphanyl)amin, HN(PPh2)2 (1), reagiert mit AgCl zu dem Komplex HN(PPh2AgCl)2 (5), für den aufgrund spektroskopischer Daten im Festzustand die dimere Clusterstruktur Ag4Cl4[HN(PPh2)2]2 angenommen wird. Die Umsetzung von 5 mit LiN(PPh2)2 (2) in Dioxan liefert die bereits bekannte Verbindung [N(PPh2AgPh2P)2N] (8) und den neuen, gelb‐grünen Komplex [Ag(μ‐Ph2PNPPh2)2(μ‐Ph2PNHPPh2)Ag] · Dioxan (7 · Dioxan), von dem eine Kristallstrukturanalyse angefertigt wurde. Sie zeigt, daß 7 · Dioxan eine Bicyclo[3.3.3]undecan‐Struktur besitzt, in der die Silberatome die seltene trigonal‐planare Koordination einnehmen. Der (AgAg)‐Abstand beträgt 281,6(1) pm und deutet auf eine Wechselwirkung zwischen den Silberatomen hin. Das Dioxan ist über eine Wasserstoffbrückenbindung an die NH‐Gruppe des koordinierten HN(PPh2)2 gebunden. Mit ClPPh2 bildet 8 N(PPh2AgCl)3 (12), welches auch durch direkte Reaktion von N(PPh2)3 (3) mit Silber(I)‐chlorid erhältlich ist. Alle Verbindungen wurden, soweit möglich, durch IR‐, Raman‐, 1H‐NMR‐, 31P{1H}‐NMR‐, 13C{1H}‐NMR‐ und Massenspektren charakterisiert.

Abstract While the reaction of anhydrous iron(III) chloride with the chelate ligand [(C6H5)2P(O)]2NH (6) is an efficient way to synthesize the new tricyclic compound imido-tetraphenyl-diphosphinato-O,O′iron(III), [Fe{O-P(Ph2)=N-P(Ph2)=O}3] (4), treatment of [(C6H5)2P]2NLi (1) with anhydrous iron(III) fluoride in THF represents a simple route to obtain the phosphorus-phosphorus connected species Ph2P-N=PPh2-PPh2=N-PPh2(7). Both compounds were charac­terized by X-ray crystallography, 1H ,31P {1H}, 13C {1H} NMR, IR, Raman and mass spectra.

Bis(diphenylphosphanyl)amine HN(PPh(2))(2) (1) reacts with AgCl to the complex HN(PPh(2)AgCl)(2) (5) for which in the solid state the cluster structure Ag4Cl4[HN(PPh(2))(2)](2) is assumed. Reaction of 5 with LiN(PPh(2))(2) (2) gives the known [N(PPh(2)AgPh(2)P)(2)N] (8) and the new complex [Ag(mu-Ph(2)PNPPh(2))(2)(mu-Ph(2)PNHPPh(2))Ag]. dioxane (7 . dioxane). The compound 7 . dioxane has been characterized by x-ray diffraction. The molecules are found to contain a bicyclo[3.3.3]undecane-type structure with trigonal planar coordinated silver atoms, which are separated by 281,6(1) pm. the dioxane is bound via H-bridge bond to the NH group of the coordinated HN(PPh(2))(2). Treatment of 8 with ClPPh(2) yields N(PPh(2)AgCl)(3) (12), which has also been obtained by the reaction of n(PPh(2))(3) (3) with silver chloride. All the compounds have been characterized, so far as possible, by IR, Raman, H-1 NMR, P-31{1H}NMR, C-13{1H} NMR and mass spectroscopy.

Reaction of Co2(CO)6(μ-η2,η2-HOCH2-CCCH2OH-C,C′) (5) with Ph2PNHPPh2 [bis(diphenylphosphino)amine, dppa, (2), P = C6H5] in toluene at 60°C gives [Co+1(CO)2{Ph2PNP(O)Ph⊖2 − P}(Ph2PNHPPh2)] (6), in which the ligand dppa was partially oxidized and deprotonated. Recrystallization of 6 from DMSO/methanol/n-hexane yields 6 · 2 CH3OH. The structure of 6 · 2CH3OH was determined by X-ray crystallography. The starting material 5 and 6 · 2 CH3OH were also characterized by 1H NMR, 13C{1H} NMR, 31P{1H} NMR and IR spectroscopy.

Reaction of Co-2(Co)(6)(mu-eta(2),eta(2)-HOCH2-C=C-CH2OH-C,C') (5) with Ph(2)P-NH-PPh(2)[bis(diphenylphosphino)amine, dppa, (2), Ph=C6H5] in toluene at 60 degrees C gives [Co+1(CO)(2){Ph(2)P - N - P(O)Ph(2)(c)ircle minus)-P)(Ph(2)P-NH-PPh(2))] (6), in which the ligand dppa was partially oxidized and deprotonated. Recrystallisation of 6 from DMSO/methanol/n-hexane yields 6 . 2 CH3OH. The structure of 6 . 2CH(3)OH was determined by X-ray crystallography. The starting material 5 and 6 . 2CH(3)OH were also characterized by H-1 NMR, C-13{1H} NMR, P-31{H-1} NMR and IR spectroscopy.