Probing the Isolobal Relation between Cp'''NiP3 and White Phosphorus by Experimental Charge Density Analysis.

An in-depth analysis of the description of bonding within Cp'''Ni-cyclo-P3 (Cp'''=1,2,4-tri-tert-butylcyclopentadienyl, [Ni]P3) employing X-ray diffraction based multipolar modeling, density functional theory (DFT) as well as an "experimental wavefunction" obtained from X-ray restrained wavefunction (XRW) fitting is presented. The results are compared to DFT calculations on white phosphorus - an isolobal analogue to [Ni]P3. A complementary bonding analysis shows insights into the reactivity of [Ni]P3. The isolobal principle is reflected in every aspect of our analysis and the employed methods seamlessly predict the differences in reactivity of [Ni]P3 and P4. Crystallographic modeling, solid-state NMR, and DFT calculations describe the dynamic behavior of the cyclo-P3 unit in the title molecule.

Three- and Five-Membered Anionic Chains of Pnictogenylboranes.

An unprecedented family of three- and five-membered substituted anionic derivatives of parent pnictogenylboranes is herein reported. Reacting various combinations of the pnictogenylboranes H2 E'-BH2 -NMe3 (E'=P, As) with pnictogen-based nucleophiles MER1R2 (E=P, As; R1=H, R2=t Bu; R1=R2=Ph; M=Na, K) allows for the isolation of the unsymmetrical products [Na(18-crown-6)][H2 E'-BH2 -EHt Bu] (3: E=E'=P; 4: E=E'=As; 5: E=As, E'=P) and [M(C)][H2 E'-BH2 -EPh2 ] (7: E=E'=P, M=Na, C=18-crown-6; 8: E=E'=As; M=K, C=[2.2.2]cryptand; 9: E=P, E'=As, M=Na, C=[2.2.2]cryptand; 10: E=As, E'=P, M=K, C=[2.2.2]cryptand). [Na(18-crown-6)][H2 As-BH2 -t BuPH-BH3 ] (6) is only accessible by a different pathway, using t BuPH2 , BH3 ⋅ SMe2 and NaNH2 as starting materials. Additionally, the synthesis of symmetrical diphenyl-substituted compounds [M(18-crown-6)][Ph2 E-BH2 -EPh2 ] (11: E=P, M=Na; 12: E=As, M=K) is reported which can be regarded as isostructural inorganic, negatively charged analogs of dppm (1,1-bis(diphenylphosphino)methane) and dpam (1,1-bis(diphenylarsino)methane). Furthermore, an elongation of the pnictogen boron backbone in compounds 3, 7 and 9' (similar compound to 9, stabilized however by 18-crown-6), is attainable by reacting them with the pnictogenylboranes H2 E'-BH2 -NMe3 leading to corresponding five-membered chain-like compounds [Na(18-crown-6)][H2 E-BH2 -R1R2P-BH2 -E'H2 ] (E=E'=P, R1=H, R2=t Bu (13); E=E'=P, R1=R2=Ph (14); E=E'=As, R1=R2=Ph (15); E=P, E'=As, R1=R2=Ph (16)). Finally, the thermodynamics of the reaction pathways were evaluated by quantum chemical computations.

Paramagnetic Molecular Semiconductors Combining Anisotropic Magnetic Ions with TCNQ Radical Anions.

We report the synthesis, magnetic properties, and transport properties of paramagnetic metal complexes, [Co(DMF)4(TCNQ)2](TCNQ)2 (1), [La(DMF)8(TCNQ)](TCNQ)5 (2), and [Nd(DMF)7(TCNQ)](TCNQ)5 (3) (DMF = N,N-dimethylformamide, TCNQ = 7,7,8,8-tetracyanoquinodimethane). All three compounds contain fractionally charged TCNQδ- anions (0 < δ < 1) and mononuclear complex cations in which the coordination environment of a metal center includes several DMF molecules and one or two terminally coordinated TCNQδ- anions. The coordinated TCNQδ- anions participate in π-π stacking interactions with noncoordinated TCNQδ- anions, forming columnar substructures that provide efficient charge-transporting pathways. As a result, temperature-dependent conductivity measurements demonstrate that all three compounds exhibit semiconducting behavior.

Cationic Functionalisation by Phosphenium Ion Insertion.

The reaction of [Cp'''Ni(η3 -P3 )] (1) with in situ generated phosphenium ions [RR'P]+ yields the unprecedented polyphosphorus cations of the type [Cp'''Ni(η3 -P4 R2 )][X] (R=Ph (2 a), Mes (2 b), Cy (2 c), 2,2'-biphen (2 d), Me (2 e); [X]- =[OTf]- , [SbF6 ]- , [GaCl4 ]- , [BArF ]- , [TEF]- ) and [Cp'''Ni(η3 -P4 RCl)][TEF] (R=Ph (2 f), tBu (2 g)). In the reaction of 1 with [Br2 P]+ , an analogous compound is observed only as an intermediate and the final product is an unexpected dinuclear complex [{Cp'''Ni}2 (µ,η3 :η1 :η1 -P4 Br3 )][TEF] (3 a). A similar product [{Cp'''Ni}2 (µ,η3 :η1 :η1 -P4 (2,2'-biphen)Cl)][GaCl4 ] (3 b) is obtained, when 2 d[GaCl4 ] is kept in solution for prolonged times. Although the central structural motif of 2 a-g consists of a "butterfly-like" folded P4 ring attached to a {Cp'''Ni} fragment, the structures of 3 a and 3 b exhibit a unique asymmetrically substituted and distorted P4 chain stabilised by two {Cp'''Ni} fragments. Additional DFT calculations shed light on the reaction pathway for the formation of 2 a-2 g and the bonding situation in 3 a.

Low-Valence Anionic α-Diimine Iron Complexes: Synthesis, Characterization, and Catalytic Hydroboration Studies.

The synthesis of rare anionic heteroleptic and homoleptic α-diimine iron complexes is described. Heteroleptic BIAN (bis(aryl)iminoacenaphthene) complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] were synthesized by reduction of the [(BIAN)FeBr2] precursor complex using stoichiometric amounts of potassium graphite in the presence of the corresponding olefin. The electronic structure of these paramagnetic species was investigated by numerous spectroscopic analyses (NMR, EPR, 57Fe Mössbauer, UV-vis), magnetic measurements (Evans NMR method, SQUID), and theoretical techniques (DFT, CASSCF). Whereas anion 1 is a low-spin complex, anion 2 consists of an intermediate-spin Fe(III) center. Both complexes are efficient precatalysts for the hydroboration of carbonyl compounds under mild reaction conditions. The reaction of bis(anthracene) ferrate(1-) gave the homoleptic BIAN complex 3-[K([18]c-6)(thf)], which is less catalytically active. The electronic structure was elucidated with the same techniques as described for complexes 1-[K([18]c-6)(thf)0.5] and 2-[K([18]c-6)(thf)2] and revealed an Fe(II) species in a quartet ground state.

Stabilization of Pentaphospholes as η5 -Coordinating Ligands.

Electrophilic functionalisation of [Cp*Fe(η5 -P5 )] (1) yields the first transition-metal complexes of pentaphospholes (cyclo-P5 R). Silylation of 1 with [(Et3 Si)2 (µ-H)][B(C6 F5 )4 ] leads to the ionic species [Cp*Fe(η5 -P5 SiEt3 )][B(C6 F5 )4 ] (2), whose subsequent reaction with H2 O yields the parent compound [Cp*Fe(η5 -P5 H)][B(C6 F5 )4 ] (3). The synthesis of a carbon-substituted derivative [Cp*Fe(η5 -P5 Me)][X] ([X]- =[FB(C6 F5 )3 ]- (4 a), [B(C6 F5 )4 ]- (4 b)) is achieved by methylation of 1 employing [Me3 O][BF4 ] and B(C6 F5 )3 or a combination of MeOTf and [Li(OEt2 )2 ][B(C6 F5 )4 ]. The structural characterisation of these compounds reveals a slight envelope structure for the cyclo-P5 R ligand. Detailed NMR-spectroscopic studies suggest a highly dynamic behaviour and thus a distinct lability for 2 and 3 in solution. DFT calculations shed light on the electronic structure and bonding situation of this unprecedented class of compounds.

Di-tert-butyldiphosphatetrahedrane: Catalytic Synthesis of the Elusive Phosphaalkyne Dimer.

While tetrahedranes as a family are scarce, neutral heteroatomic species are all but unknown, with the only reported example being AsP3 . Herein, we describe the isolation of a neutral heteroatomic X2 Y2 molecular tetrahedron (X, Y=p-block elements), which also is the long-sought-after free phosphaalkyne dimer. Di-tert-butyldiphosphatetrahedrane, (tBuCP)2 , is formed from the monomer tBuCP in a nickel-catalyzed dimerization reaction using [(NHC)Ni(CO)3 ] (NHC=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (IMes) and 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (IPr)). Single-crystal X-ray structure determination of a silver(I) complex confirms the structure of (tBuCP)2 . The influence of the N-heterocyclic carbene ligand on the catalytic reaction was investigated, and a mechanism was elucidated using a combination of synthetic and kinetic studies and quantum chemical calculations.

The Parent Diarsene HAs=AsH as Side-on Bound Ligand in an Iron Carbonyl Complex.

The terminal diarsene HAs=AsH ligand attracts special interest concerning its bonding relation in comparison to its isolable relative, ethene. Herein, by the methanolysis of [{Fe(CO)4 }As(SiMe3 )3 ] (1) the synthesis of [{Fe(CO)4 }(η2 -As2 H2 )] (2) is reported, containing a parent diarsene as unprecedented side-on coordinated ligand. Following this synthetic route, also the D-labeled complex [{Fe(CO)4 }(η2 -As2 D2 )] (2D) could be isolated. The electronic structure and bonding situation of 2 was elucidated by DFT calculations revealing that 2 is best described as an olefin-like complex. Moreover, the reactivity of 2 towards the Lewis acids [{M(CO)5 }(thf)] (M=Cr, W) was investigated, leading to the complexes [Fe(CO)4 AsHW(CO)5 ]2 (3) and [{Fe(CO)4 }2 AsH{Cr(CO)5 }] (4), respectively.

Macrocyclic Triruthenium Complexes Having Electronically Coupled Mixed-Valent States.

5-Ethynyl-2-furancarboxylic acid and 3-ethynylbenzoic acid self-assemble with [HRu(CO)Cl(PiPr3 )2 ] to form macrocyclic C3 -symmetric triangular triruthenium alkenyl complexes [{Ru(CO)(PiPr3 )2 (CH=CHArCOO)}3 ] (Ar=C6 H4 : 1-B, Ar=C4 H2 O: 1-F), which were characterized by multinuclear NMR spectroscopy, high-resolution ESI mass spectrometry, and, in the case of 1-B, by X-ray crystallography. Electrochemical studies indicate that the macrocycles are oxidized in three consecutive one-electron steps. The mixed-valent states obtained by electrochemical or chemical oxidation show signs of valence delocalization, which makes these complexes rare examples of molecule-based conductive loops with through-bond charge delocalization.

Depolymerization of Poly(phosphinoboranes): From Polymers to Lewis Base Stabilized Monomers.

We report on depolymerization reactions of poly(phosphinoboranes). The cleavage of the polymers [H2 PBH2 ]n (2 a), [tBuHPBH2 ]n (2 c), [PhHPBH2 ]n (2 e) and the oligomer [Ph2 PBH2 ]n (2 b), with strong Lewis bases (LBs), in particular with NHCs, leads to the corresponding monomeric phosphanylboranes R1 R2 PBH2 LB. It is observed that the depolymerization depends on the strength and stability of the LBs as well as on the substitution pattern of the poly(phosphinoboranes). The solid state structures of the monomeric phosphinoboranes H2 PBH2 NHCMe (NHC=N-heterocyclic carbene) (4 a), H2 PBH2 NHCdipp (5 a) and tBuHPBH2 NHCMe (4 c) were determined. DFT calculations support the experimentally observed reaction behavior.

Gold(I) Complexes Containing Phosphanyl- and Arsanylborane Ligands.

The structural and photophysical properties of a series of new AuI compounds have been studied. The reactions of AuCl(tht) with the phosphanyl- and arsanylboranes RR' EBH2 NMe3 (E=P, As; R=H, Ph; R'=H, Ph, tBu) afford the complexes [AuCl(RR' EBH2 NMe3 )]. In the solid state, [AuCl(H2 PBH2 NMe3 )]2 (2 a) is a dimer showing unsupported intermolecular aurophilic interactions with short Au⋅⋅⋅Au distances. In contrast, [AuCl(H2 AsBH2 NMe3 )]n (2 b) aggregates to form 1D chains. Organic substituents on the pnictogen atoms lead to discrete molecules in [AuCl(RR' PBH2 NMe3 )] (2 c: R=H, R'=tBu; 2 d: R=R'=Ph). To increase the aurophilicity, the ionic homoleptic complexes [Au(RR' EBH2 NMe3 )2 ][AlCl4 ] (3 a-d) have been synthesized, for which 3 a,b form chains in the solid state and exhibit luminescence. The emissions show a drastic redshift with temperature decrease, correlating with decreasing Au⋅⋅⋅Au distances. DFT calculations provide insight into the bonding situation of the products.

Transfer Reagent for Bonding Isomers of Iron Complexes.

The cothermolysis of As4 and [Cp″2Zr(CO)2] (Cp″ = η5-C5H3tBu2) results in the formation of [Cp″2Zr(η1:1-As4)] (1) in high yields and the arsenic-rich complex [(Cp″2Zr)(Cp″Zr)(µ,η2:2:1-As5)] (2) as a minor product. In contrast to yellow arsenic, 1 is a light-stable, weighable and storable arsenic source for subsequent reactions. The transfer reaction of 1 with [Cp‴Fe(µ-Br)]2 (Cp‴ = η5-C5H2tBu3) yields the unprecedented bond isomeric complexes [(Cp‴Fe)2(µ,η4:4-As4)] (3a) and [(Cp‴Fe)2(µ,η4:4-cyclo-As4)] (3b). In contrast, the analogous reaction with the CpBn derivative [CpBnFe(µ-Br)]2 (CpBn = η5-C5(CH2(C6H5)5) leads exclusively to the triple decker complex [(CpBnFe)2(µ,η4:4-As4)] (4) possessing the tetraarsabutadiene-type ligand analogous to 3a. To elucidate the stability of the bonding isomers 3a and 3b, DFT calculations were performed. The oxidation of 4 with AgBF4 affords [(CpBnFe)2(µ,η5:5-As5)][BF4] (5), which is a product expanded by one arsenic atom, instead of the expected complex [(CpBnFe)2(µ,η4:4-cyclo-As4)]+.

Coordination Behavior of [Cp''2 Zr(η1:1 -P4 )] towards Different Lewis Acids.

A detailed method for the preparation of [Cp''2 Zr(η1:1 -P4 )] (1) is presented. The coordination behavior of 1 towards Lewis acidic transition metal complexes of tungsten, manganese, and iron, respectively, and main group compounds (AlMe3 , AlEt3 ) was investigated in detail by computational and experimental studies. In doing so, a series of unprecedented complexes with different coordination modes and multiple coordination numbers of the tetraphosphabicyclo[1.1.0]butane framework were synthesized. All products, as well as the starting materials, were comprehensively characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray structural analysis.

Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments.

The redox chemistry of [Cp*Fe(η5 -As5 )] (1, Cp*=η5 -C5 Me5 ) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η5 -P5 )]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel Asn scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme)2 ][{Cp*Fe(µ,η2:2 -As2 )}2 ] (2) and the arsenic-rich complexes [K(dme)3 ]2 [(Cp*Fe)2 (µ,η4:4 -As10 )] (3), [K(dme)2 ]2 [(Cp*Fe)2 (µ,η2:2:2:2 -As14 )] (4), and [K(dme)3 ]2 [(Cp*Fe)4 (µ4 ,η4:3:3:2:2:1:1 -As18 )] (5). Compound 4 and the polyarsenide complex 5 are the largest anionic Asn ligand complexes reported thus far. Complexes 2-5 were characterized by single-crystal X-ray diffraction, 1 H NMR spectroscopy, EPR spectroscopy (2), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(η5 -As5 )]- , which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe)2 (µ,η4:4 -As10 )]2- .

Dibenzo[b,f][1,4]oxazepines and dibenzo[b,e]oxepines: Influence of the chlorine substitution pattern on the pharmacology at the H1R, H4R, 5-HT2AR and other selected GPCRs.

Inspired by VUF6884 (7-Chloro-11-(4-methylpiperazin-1-yl)dibenzo[b,f][1,4]oxazepine), reported as a dual H1/H4 receptor ligand (pKi: 8.11 (human H1R (hH1R)), 7.55 (human H4R (hH4R))), four known and 28 new oxazepine and related oxepine derivatives were synthesised and pharmacologically characterized at histamine receptors and selected aminergic GPCRs. In contrast to the oxazepine series, within the oxepine series, the new compounds showed high affinity to the hH1R (pKi: 6.8-8.7), but no or moderate affinity to the hH4R (pKi:≤5.3). For one oxepine derivative (1-(2-Chloro-6,11-dihydrodibenzo[b,e]oxepin-11-yl)-4-methylpiperazine), the enantiomers were separated and the R-enantiomer was identified as the eutomer at the hH1R (pKi: 8.83 (R), 7.63 (S)) and the guinea-pig H1R (gpH1R) (pKi: 8.82 (R), 7.41 (S)). Molecular dynamic studies suggest that the tricyclic core of the compounds is bound in a similar mode into the binding pocket, as described for doxepine in the hH1R crystal structure. Moreover, docking studies of all oxepine derivatives at the hH1R indicate that the oxygen and the position of the chlorine in the tricyclic core determines, if the R- or the S-enantiomer is the eutomer. For some of the oxazepines and oxepines the affinity to other aminergic GPCRs is in the same range as to hH1R or hH4R, thus, those compounds have to be classified as dirty drugs. However, one oxazepine derivative (3,7-Dichloro-11-(4-methylpiperazin-1-yl)dibenzo[b,f][1,4]oxazepine was identified as dual hH1/h5-HT2A receptor ligand (pKi: 9.23 (hH1R), 8.74 (h5-HT2AR), ≤7 at other analysed GPCRs), whereas one oxepine derivative (1-(3,8-Dichloro-6,11-dihydrodibenzo[b,e]oxepin-11-yl)-4-methylpiperazine) was identified as selective hH1R antagonist (pKi: 8.44 (hH1R), ≤6.7 at other analyzed GPCRs). Thus, the pharmacological results suggest that the oxazepine/oxepine moiety and additionally the chlorine substitution pattern toggles receptor selectivity and specificity.

Modulation of Intersystem Crossing Rate by Minor Ligand Modifications in Cyclometalated Platinum(II) Complexes.

Photophysical properties of four new platinum(II) complexes comprising extended ppy (Hppy = 2-phenylpyridine) and thpy (Hthpy = 2-(2'-thienyl)pyridine) cyclometalated ligands and acetylacetonate (acac) are reported. Substitution of the benzene ring of Pt-ppy complexes 1 and 2 with a more electron-rich thiophene of Pt-thpy complexes 3 and 4 leads to narrowing of the HOMO-LUMO gap and thus to a red shift of the lowest energy absorption band and phosphorescence band, as expected for low-energy excited states of the intraligand/metal-to-ligand charge transfer character. However, in addition to these conventional spectral shifts, another, at first unexpected, substitution effect occurs. Pt-thpy complexes 3 and 4 are dual emissive showing fluorescence about 6000 cm(-1) (∼0.75 eV) higher in energy relative to the phosphorescence band, while for Pt-ppy complexes 1 and 2 only phosphorescence is observed. For dual-emissive complexes 3 and 4, ISC rates kISC are estimated to be in order of 10(9)-10(10) s(-1), while kISC of Pt-ppy complexes 1 and 2 is much faster amounting to 10(12) s(-1) or more. The relative intensities of the fluorescence and phosphorescence signals of Pt-thpy complexes 3 and 4 depend on the excitation wavelength, showing that hyper-intersystem crossing (HISC) in these complexes is observably significant.

Condensation Reactions of Chlorophosphanes with Chalcogenides.

A high-yielding and facile synthesis for diphosphane monochalcogenides (1(Ch)((R))) and their constitutional isomers, diphosphanylchalcoganes (2(Ch)((R))), was developed, featuring a condensation reaction between chlorophosphanes (R2PCl) and sodium chalcogenides (Na2Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either 1(Ch)((R)) (R2(Ch)PPR2) or 2(Ch)((R)) (Ch(PR2)2) depending upon the steric demand of the substituents R. Reaction pathways consistent with the distinct reaction outcomes are proposed. The application of 1(Ch)((R)) and 2(Ch)((R)) as an interesting class of ligands is exemplarily demonstrated by the preparation of selected transition metal complexes.

Pentaarylcyclopentadienyl Iron, Cobalt, and Nickel Halides.

The preparation of new stable half-sandwich transition metal complexes, having a bulky cyclopentadienyl ligand C5(C6H4-4-Et)5 (Cp(Ar1)) or C5(C6H4-4-nBu)5 (Cp(Ar2)), is reported. The tetrahydrofuran (THF) adduct [Cp(Ar1)Fe(µ-Br)(THF)]2 (1a) was synthesized by reacting K[Cp(Ar1)] with [FeBr2(THF)2] in THF, and its molecular structure was determined by X-ray crystallography. Complex 1a easily loses its coordinated THF molecules under vacuum to form the solvent-free complex [Cp(Ar1)Fe(µ-Br)]2 (1b). The analogous complexes [Cp(Ar1)Co(µ-Br)]2 (2), [Cp(Ar1)Ni(µ-Br)]2 (3), and [Cp(Ar2)Ni(µ-Br)]2 (4) were synthesized from CoBr2 and [NiBr2(1,2-dimethoxyethane)]. The mononuclear, low-spin cobalt(III) and nickel(III) complexes [Cp(Ar2)MI2] (5, M = Co; 6, M = Ni) were prepared by reacting the radical Cp(Ar2) with NiI2 and CoI2. The complexes were characterized by NMR and UV-vis spectroscopies and by elemental analyses. Single-crystal X-ray structure analyses revealed that the dimeric complexes 1a, 1b, and 3 have a planar M2Br2 core, whereas 2 and 4 feature a puckered M2Br2 ring.

Anionic Chains of Parent Pnictogenylboranes.

We report on the synthesis and structural characterization of unprecedented anionic parent compounds of mixed Group 13/15 elements. The reactions of the pnictogenylboranes H2 E-BH2 ⋅NMe3 (1 a=P, 1 b=As) with phosphorus and arsenic centered nucleophiles of the type [EH2 ]- (E=P, As) lead to the formation of compounds of the type [H2 E-BH2 -E'H2 ]- (2: E=E'=P; 3: E=E'=As; 4: E=P, E'=As) containing anionic pnictogen-boron chain-like units. Furthermore, a longer 5-membered chain species [H2 As-BH2 -PH2 -BH2 -AsH2 ]- (5) and a cyclic compound [NHCdipp -H2 B-PH2 -BH2 -NHCdipp ]+ [P5 B5 H19 ]- (6) containing a n-butylcyclohexane-like anion were obtained. All the compounds have been characterized by X-ray structure analysis, multinuclear NMR spectroscopy, IR spectroscopy, and mass spectrometry. DFT calculations elucidate their high thermodynamic stability, the charge distribution, and give insight into the reaction pathway.

Reaction of tungsten-phosphinidene and -arsinidene complexes with carbodiimides and alkyl azides: a straightforward way to four-membered heterocycles.

The reaction of the phosphinidene and arsinidene complexes [Cp*E{W(CO)5 }2 ] (E=P (1 a), As (1 b); Cp*=C5 Me5 ) with carbodiimides leads to the new four-membered heterocycles of the type [Cp*C(NR)2 E{W(CO)5 }2 ] (E=P: R=iPr (2 a), Cy (3 a); E=As: R=iPr (2 b), Cy (3 b)). The reaction of phosphinidene complex 1 a with alkyl azides yields the triazaphosphete derivatives [Cp*P{W(CO)5 }N(R)NN{W(CO)5 }] (R=Hex, Cy) (4). These unprecedented N3 P four-membered triazaphosphete complexes can be regarded as stabilized intermediates of the Staudinger reaction, which have not been previously isolated. All of the isolated products were characterized by NMR, IR spectroscopy, mass spectrometry, and by single-crystal X-ray diffraction analysis.