PMe2 Ph Research Articles

Diferrocenyltriphosphines 1: five-coordinate ruthenium complexes

The ligand bis-1-(1′-diphenylphosphinoferrocenyl)phenylphosphine, triphosfer, reacts with dichlorotris-triphenylphosphineruthenium(II) to give the complex [(triphosfer)RuCl 2], ( 17), in almost quantitative yield. This complex reacts with CO at ambient temperature to afford [(triphosfer)Ru(CO)Cl 2]. Three related complexes, [{(η-R 2PC 5H 4)Fe–μ 2-(η-C 5H 4P(R′)η-C 5H 4)Fe(η-C 5H 4R 2)}RuCl 2], R,R′=Ph, iPr ( 18–20), exhibit identical chemical properties. Reaction of complexes 17–20 with excess PMe 2Ph results in the deligation of the ferrocene ligand. The electrochemistry shows that while the diferrocenyltriphosphine ligands undergo a single two-electron oxidation, irreversible in character, complexes ( 17–19) exhibit two separated one-electron oxidations having features of chemical reversibility. This data suggests that while within the ligands no electronic communication exists between the two ferrocene subunits, complexation with RuCl 2 allows communication between the two ferrocenes. The single crystal X-ray structure of [(triphosfer)RuCl 2] has been determined.

CF bond activation in perfluorobenzothiolate compounds of Os(III). X-ray structures of [formula omitted], [Os(SC 6F 5) 2( o-S 2C 6F 4)(PMe 2Ph)] and [Os(C 6F 5) 2( o-S 2C 6F 4)(PMe 2Ph) 2

Thermolysis of [ Os(SC 6F 4(F -2))(SC 6F 5) 2)(PMe 2Ph 2) ] ( 1) in refluxing toluene affords [Os(SC 6F 5) 2( o-S 2C 6F 4)(PMe 2Ph)] ( 2) and [Os(C 6F 5) 2( o-S 2C 6F 4)(PMe 2Ph) 2] ( 3) through a process involving CF cleavage as well as CS bond formation. The X-ray structures of 1, 2 and 3 have been determined. In the solid state compound 1 shows a CF → Os interaction.

New thiophene metallacarbaborane compounds of palladium and platinum: X-ray structures of 1-C 4H 3S-3-(cod)-3,1,2-M-C 2B 9H 10, 1-C 4H 3S-3,3-(PMe 2Ph) 2-3,1,2-Pt–C 2B 9H 10 and 1-C 4H 3S-3,3-(PPh 2CH 2CH 2Ph 2)-3,1,2-Pd-C 2B 9H 10 (M=Pt or Pd)

The icosahedral metallacarboranes [1-C 4H 3S-3,3-(PMe 2Ph) 2-3,1,2-Pt-C 2B 9H 10], [1-C 4H 3S-3-(cod)-3,1,2-M-C 2B 9H 10] (M=Pt or Pd) and [1-C 4H 3S-3,3-(PPh 2CH 2CH 2Ph 2)-3,1,2-Pd-C 2B 9H 10] were synthesised from Tl 2[7-(C 4H 3S)-7,8- nido-C 2B 9H 10], [PtCl 2(PMe 2Ph) 2], [MCl 2(cod)] (M=Pt or Pd) and [PdCl 2(PMe 2Ph) 2], respectively (cod, cyclo-octa-1,5-diene). Their single crystal X-ray structures have been completed and their molecular structures are described.

Synthesis of cis- and trans-dichloro(dimethylphenylphosphine)-(1-methyl-1,4,5,6-tetrahydropyrimidine)platinum(II) and their spectral and structural characterization

Interaction of [{Pt( μ-Cl)Cl(PMe 2Ph)} 2] with 1-methyl-1,4,5,6-tetrahydropyrimidine, L (R=Me), in boiling toluene produced a mixture of cis- and trans- isomers of [PtCl 2(PMe 2Ph){ N=CH(Me)CH 2CH 2C H 2}]; trans-complex 2 isomerizes to give thermodynamically more stable corresponding cis-complex 1 in boiling ethanol. Spectroscopic and X-ray diffraction data permit generalizations about cis- and trans- isomeric pairs to be made. In addition, the trans influence of the ligand L is reliably assessed.

New dithiocarbamate compounds of manganese carbonyl and a zinc polymer

The reaction of [EtO 2CN=CS 2C {N (H) CO 2Et} {S 2CN (H) CO 2Et} ] , 1 with Mn 2 (CO) 9NCMe yielded the dithiocarbamate complex Mn (CO) 4 [S 2CN (H) CO 2Et] , 2 which was characterized structurally in the form of its phosphine derivative Mn (CO) 3 (PMe 2Ph) [S 2CN (H) CO 2Et] , 3. Compound 3 was found to contain a chelating dithiocarbamato ligand with a cis-positioned phosphine ligand. Compound 1 also reacts with zinc acetylacetonate to yield the zinc dithiocarbamate complex Zn ( μ- S, S-S 2CN (H) CO 2Et) ( μ- O, S-S 2CN (H) CO 2Et) , 4. Compound 4 forms a helical polymer in the solid state with the zinc ions linked by bridging dithiocarbamate ligands. Compound 1 appears to be a good source of the ethoxycarbonylthiocarbamate ligand.

The preparation, crystal structure and some reaction chemistry of Bromo ( η5-penta- phenylcyclopentadienyl) dicarbonylosmium (II) , [Os ( η5-C 5Ph 5) (CO) 2Br

The preparation and characterisation of [Os ( η 5-C 5Ph 5) (CO) 2Br] (1) are described ; this complex is the first reported C 5 Ph − 5 derivative of osmium. A single crystal X-ray diffraction study of (1) (refined to R = 0.040, R w = 0.043) is also reported. The related complexes, [Os { η 5-C 5Ph 4 ( p- tBuC 6H 4) } (CO) 2Br] (2) and [Os { η 5-C 5 ( p-MeC 6H 4) 5} (CO) 2Br] (3) , have also been prepared. Carbonyl substitution of (1) in tetrahydrofuran following treatment with Me 3NO afforded [Os ( η 5-C 5Ph 5) (CO) (L) Br] (L = PMe 2Ph (4) , P (OEt) 3 (5) , P (OCH 2) 3CCH 3 (6) and tBuNC (7) ) . A single crystal X-ray diffraction study of (6) (refined to R = 0.066, R w = 0.073) is described.

Iron dinitrosyl complexes of TCNE: a synthetic, X-ray crystallographic, high field NMR and electrochemical study

Treatment of Fe(NO) 2[PR 3](CO) with tetracyanoethylene (TCNE) in diethyl ether leads to the formation of Fe(NO) 2[PR 3]( η 2-TCNE), where PR 3=P(OCH 3) 3, 1, P( n-Bu) 3, 2, PMe 2Ph, 3, and PEt 2Ph, 4. An X-ray crystallographic study of 1 shows the iron to be situated in a nearly tetrahedral environment with a π-bonded tetracyanoethylene and two linearly bound nitrosyl groups. From the ambient-temperature NMR spectral data, it is evident that there exist two non-equivalent cyanocarbon environments, indicating that the rotation about the Fe-TCNE π-bond is slowed at room temperature; variable-temperature NMR studies on Fe(NO) 2[P(OMe) 3]( η 2-TCNE), 1, yielded an activation energy barrier of approximately 18.1±0.5 kcal mol −1 for this rotational process. Electrochemical studies revealed that the neutral Fe(NO) 2[PR 3]( η 2-TCNE) complexes undergo irreversible reductions at positively shifted potentials, relative to the related Fe(NO) 2[PR 3](CO) complexes. Moreover, a trend toward cathodic shift of the reduction potentials with increasing phosphine p K a has been observed. The high energy barrier for alkene rotation and the shift towards positive reduction potentials are rationalized in terms of a strong π-interaction between the iron center and TCNE.

Macropolyhedral boron-containing cluster chemistry. [PtMe 2(PMe 2Ph) 2] as a cluster metallating agent. Isolation and characterisation of nineteen-vertex [(PMe 2Ph)HPt- η4- syn-B 18H 19(PMe 2Ph)] and eighteen-vertex [(PMe 2Ph) 2PtS 2B 15H 14(NHCOMe

[PtMe 2(PMe 2Ph) 2] reacts quantitatively with [ nido-B 10H 14], [ arachno-4-SB 8H 12] and [ nido-7-SB 10H 12] to give [(PMe 2Ph) 2PtB 10H 12], [(PMe 2Ph) 2PtSB 8H 10] and [(PMe 2Ph) 2PtSB 10H 10]. With [ syn-B 18H 22] it gives nineteen-vertex [(PMe 2Ph)HPt- η 4- syn-B 18H 19(PMe 2Ph)] 1 and only smaller amounts of [(PMe 2Ph) 2Pt- η 4- syn-B 18H 20], whereas with [( anti)-9,9′-S 2B 16H 16] a complex product mixture is generated from which eighteen-vertex [(PMe 2Ph) 2PtS 2B 15H 14(NHCOMe)] 1 is isolatable after treatment with MeCN in air.

Metal-metal multiply-bonded complexes of technetium. 7 1. Oxidative decomposition of tetrachlorotetrakis(dimethylphenylphosphino) ditechnetium(II) by an aminium hexachloroantimonate(V)

TeCl 4(PMe 2Ph) 2·2SbCl 3 was isolated in low yield from the reaction of Te 2Cl 4(PMe 2Ph) 2 with 2 equiv. of [( p-BrC 6H 4) 3N][SbCl 6] in acetonitrite. Single crystals were obtained by slow evaporation of a toloune solution. The structure, determined by X-ray crystallography, is composed of infinite one-dimensional chains of an alternating sequence of TeCl 4(PMe 2Ph) 2 and (SbCl 3) 2 molecules. The individual molecular species are loosely associated through Lewis acid-base interactions between the equatorial chlorine atoms of TeCl 4(PMe 2Ph) 2 and the individual SbCl 3 units. The chains are contained by an additional weak Lewis acid-base interaction between neighboring SbCl 4 molecules. The distorted pentagonal bipyramidal coordination geometry about the antimony atom is completed by a weak π-interaction with the phenyl ring of TeCl 4(PMe 2Ph) 2. Crystal data for TeCl 4(PMe 2Ph) 2·2SbCl 4 ( 1) at 23°C: M=972.28, triclinic, Pl (No. 2), α=10.591(3), b=10.619(2), c=7.578(1) A ̊ , α=104.54(2), β=99.69(2), γ=69.92(2)°, V=771.7(3) A ̊ , Z=1 .

Solution and crystal structure of the dihydrogen complex [Ru(H 2)(H)(PMe 2Ph) 4]PF 6, an active alkyne hydrogenation catalyst

The complex [Ru(H 2)(H)(PMe 2Ph) 4]PF 6 ( 1) has been prepared by reaction of [Ru(H)(PMe 2Ph) 5] FP 6 ( 2) in THF with 1 atm H 2 and characterised by variable temperature 31P and 1H NMR. It undergoes four distinct fluxional processes listed in order of decreasing activation energy: (i) exchange of H 2 in solution with the dihydrogen ligand above 273 K; (ii) isomerisation of cis and trans isomers of 1 above 230 K; (iii) exchange of H atoms between H 2 and hydride in trans- 1 above 180 K; (iv) rapid H 2/hydride exchange in cis- 1 to below 180 K. A single crystal X-ray diffraction study of 1 at 173 K shows that the complex has the cis geometry in the solid state but does not clearly reveal the positions of the hydrogen ligands. Complex 1 starts out as a catalyst of high activity for the selective hydrogenation of 1-alkynes to 1-alkenes (RC≡CH; R= 11Bu, Ph) but it is rapidly deactivated, possibly because of formation of the enynyl complex [Ru( η 3RC 3CHR)(PMe 2Ph) 4] +. Complex 1 efficiently catalyzes the hydrogenation of internal alkynes (3-hexyne, 2-pentyne) to internal cis-alkenes with little deactivation, although some isomerisation of the alkene produced is observed. These observations are consistent with those of Nkosi, Coville, Albers and Singleton who reported that complex 2 must dissociate one PMe 2Ph ligand to produce the species active for alkyne hydrogenation. Complex 2 catalyses these hydrogenations with slower initial rates than complex 1 but deactivates less readily. In contrast to 1, complex 2 does not appear to cause the isomerisation of internal alkenes.

Thermal and photochemical substitution reactions of CpRe(PPh 3) 2H 2 and CpRe(PPh 3)H 4. Catalytic insertion of ethylene into the C-H bond of benzene

The thermal and photochemical reactions of CpRe(PPh 3) 2H 4 and CpRe(PPh 3)H 4 (Cp = η 5-C 5H 5) with PMe 3, P( p-tolyl) 3, PMe 2Ph, DMPE, DPPE, DPPM, CO, 2,6-xylylisocyanide and ethylene have been examined. While CpRe(PPh 3) 2H 2 is thermally inert, it will undergo photochemical substitution of one or two PPh 3 ligands. With ethylene, substitution is followed by insertion of the olefin into the C-H bond of benzene, giving ethylbenzene. CpRe(PPh 3)H 4 undergoes thermal loss of PPh 3, which leads to substituted products of the type CpRe(L) H 4. Photochemically, reductive elimination of dihydrogen occurs preferentially. The complex trans-CpRe(DMPE)H 2 was structurally characterized, crystallizing in the monoclinic space group P2 1/ n (No. 14) with a = 6.249(6), b = 16.671(8), c = 13.867(7) Å, β = 92.11(6)°, V = 1443.7(2.9) Å and Z = 4. The complex trans-CpRe(PMe 2Ph) 2H 2 was structurally characterized, crystallizing in the monoclinic space group P2 1/ n (No. 14) with a = 7.467(3), b = 23.874(14), c = 11.798(6) Å, β = 100.16(4)°, V = 2070.2(3.4) Å 3 and Z = 4.

Optically active transition metal compounds 113 : Synthesis of chiral carbonylnitrosylcobalt complexes with four different unidentate ligands

In a two step synthesis pairs of diastereomers Co(CO)(NO)(L)(L*), which differ only in the configuration at the cobalt atom, are obtained from Co(CO) 3(NO). L is a monodentate phosphite or phosphane and L* a monodentate optically active phosphane or isocyanide. For complex 8 (L=PPh 3, L=phenyl-tarpholane) a diastereomer ratio of 55:45 ( 8a: 8b) is found after the synthesis. For all other complexes this ratio is 50:50. By crystallization it is possible to obtain samples enriched in one of the diastereomers of 1 (L=P(OMe) 3, L*=PPh 2N(Me)CH(Me)(Ph)), 2 (L=PPh 3, L*=CNCH(Me)(Ph)), 7 (L=PMe 2Ph, L*=glyphos) and 8. The ratios achieved are 74:26 ( 1a: 1b), 79:21 ( 2a: 2b), 71:29 ( 7a: 7b) and 74:26 ( 8a: 8b). The crystal structures of six complexes were determined. For ( S Co, S C)- 2a, ( R Co, S C)- 3b and ( S Co, R C, R C)- 8a the absolute configuration could be established. The cobalt center is configurationally stable at room temperature. Epimerization is observed only at higher temperatures. 1a epimerizes in toluene-d 8 at 82.2°C with a half life of τ 1/2=43 h, 2a in benzene-d 6 at 72.9°C with τ 1/2=83 min and 7a in benzene-d 6 at 70.0°C with τ 1/2=77 min.

Oxidatively induced metal–carbon bond cleavage reactions in iridium dimethyl complexes: formation of cationic pyridine and nitrosyl iridium(III) alkyl derivatives

Reaction of [Ir(Me) 2Cp*(L)] complexes (Cp*= η 5-C 5Me 5; L=PPh 3, PMePh 2, PMe 2Ph, PMe 3) with equimolar amounts of [Fe Cp 2] + in pyridine gives methane and the corresponding cationic derivatives [Ir(Me)Cp*(L) (pyridine)] +. Reaction with an excess of NOBF 4 yields methane and [Ir(Me)Cp*(L)(NO)] 2+ (L=PMe 3, PMe 2Ph, PMePh 2) or [Ir(Me) 2Cp*(NO)] + and [Ir(Me)Cp*(L) 2] + (L=PPh 3) via the formation of the primary oxidation products [Ir(Me) 2Cp*(L)] +, which have been detected by EPR spectroscopy.

Structures of HRh(PMe 2Ph) 4 and HRh(PPh 2Me) 4

The mononuclear hydrido complexes HRh(PMe 2Ph) 4 ( 1) and HRh(PPh 2Me) 4 ( 2) have been prepared and structurally analyzed by X-ray diffraction techniques. The geometry of both compounds consists of a distorted trigonal bipyramidal arrangement of ligands around rhodium. The hydride ligands were not located crystallographically, but were predicted by potential energy calculations to be situated at the axial positions. Crystallographic details: both compounds crystallize in the triclinic space group P 1 . For HRh(PMe 2Ph) 4 ( 1): a=11.058(4), b=16.332(4), c=9.530(3) A ̊ , α=94.07(2), β=99.37(3), γ=102.21(3)°, V=1662.4(9) A ̊ 3 for Z=2; R F -0.0463, R wF =0.0496 for 3550 reflections with I>3δ(I). For HRh(PPh 2Me) 4 ( 2): a=13.061(6), b=16.672(7), c=12.150(6) A ̊ ; α=107.30(3), β=114.19(3), γ=71.45(4)°, V=2245(2) A ̊ 3 for Z=2; R F =0.0482, R wF =0.0488 for 4350 reflections with I>3δ(I).

Polyhedral oxaplatinaborane chemistry: characterisation of [9,9-(PMe 2Ph) 2- arachno-9,6-PtOB 8H 10] and its metallaborane non-oxa cognate [6,6-(PMe 2Ph) 2- arachno-6-PtB 9H 11-9-(PMe 2Ph)

Reaction of [(PMe 2Ph) 2PtB 8H 12] with KH and [{( η 5-C 5Me 5)RhCl 2} 2] followed by chromatographic separation in air unexpectedly gave the ten-vertex oxametallaborane [9,9-(PMe 2Ph) 2- arachno-9,6-PtOB 8H 10] ( 1, 11%), which has a classical arachno ten-vertex geometry with the {O} and{Pt(PMe 2Ph) 2} vertices in the prow (6)- and (9)-positions; the oxygen atom is therefore bound contiguously to boron atoms only. Reaction of [PtMe 2(PMe 2Ph) 2] with [6,9-(PMe 2Ph) 2B 10H 12] generates its ten-vertex metallaborane cognate [6,6-(PMe 2Ph) 2- arachno-6-PtB 9H 11-9-(PMe 2Ph)] ( 3, 10%), and completes a coherent B→C→N→O cluster constituent sequence. Compounds 1 and 3 are characterised by single-crystal X-ray diffraction analysis and NMR spectroscopy.

B-frame supported bimetallics. [(PMe 2ph) 2PtB 9H 11Ru( η6- isoPrC 6H 4Me)] and [(PMe 2ph) 2PtB 9H 9Ru( η6- isoPrC 6H 4Me)]; an interesting pair of electron-deficient nido and closo geometries

[7,7-(PMe 2Ph) 2-9-( η 6- iso PrC 6H 4Me)-7,9-PtRuB 9H 11] has a formal closo Wadian cluster-electron count, but a nido geometry, whereas [1-( η 6- iso PrC 6H 4Me)-4,4-(PMe 2Ph) 2-1-4-RuPtB 9H 9], which does have a closo geometry, has a formal sub- closo cluster electron count; both compounds are formed in the reaction between [6-( η 6- iso PrC 6H 4Me)- nido-6 RuB 9H 13], KH and [PtCl 2(PMe 2Ph) 2].

Synthesis and structure of binuclear complexes of palladium and platinum containing bridging diphenylphosphinate ligand

Treatment of [M 2Cl 2(μ-Cl) 2(PR 3) 2] M/PRPt/PEt 3, Pt/PBu 3, Pt/PMe 2Ph, Pt/PMePh 2, Pd/PMe 2Ph) with AgO 2PPh 2 at room temperature, gave diphenylphosphinato-bridged binuclear complexes [M 2Cl 2(μ-O 2PPh 2) 2(PR 3) 2]. These complexes were characterized by NMR spectroscopy and elemental analysis. Crystal and molecular structure of [Pt 2Cl 2(μ-O 2PPh 2) 2(PMe 2Ph) 2] has been determined by single crystal X-ray diffraction. The eight-membered metallocyclic ring “Pt 2(O 2P) 2” has a boat conformation with Pt ⋯ Pt separation of 3.2212(6) Å.

Reactivity of bimetallic dibridged complexes Cp 2Ta(H)(μ-H)(μ-PMe 2)M′(CO) 4 (M′ = Cr, Mo, W) toward two-electron donor ligands L (L = PR 3, Me 2P(CH 2) nPMe 2). Synthesis of linear trinuclear chain complexes Cp 2Ta(H) 2(μ-PMe 2)M′(CO) 4(Me 2P(CH 2) 2PMe 2)Cr(CO) 5 (M′ = Mo, W)

The reaction of the heterobimetallic phosphido- and hydrido-bridged complexes Cp 2TaH(μ-H)(μ-PMe 2)M′(CO) 4 (M′ = Cr, Mo, W) ( 1–3) with phosphines (L = PPh 2Me, PMe 2Ph) or diphosphines (L = dmpm, dmpe) leads to Cp 2Ta(H) 2(μ-PMe 2)M′(CO) 4(L) ( 1a, 1b, c, d-3b, c, d) with L regiospecifically coordinated to M′. Except for L = PPh 2Me, the reaction is stereospecific, since a cis arrangement (with respect to the PMe 2 bridge) on the M′ site is obtained. The new compounds Cp 2Ta(H) 2(μ-PMe 2)M′ (CO) 4(Me 2P(CH 2) 2PMe 2) (M′ = Mo, W) are able to bind [Cr(CO) 5] fragments affording the linear trinuclear chain compounds Cp 2Ta(H) 2(μ-PMe 2)M′(CO) 4(Me 2P(CH 5) ( 4,5). All new complexes have been fully characterized by NMR and IR spectroscopy, and by their elemental analyses.

Monohydride complexes of W (IV) containing bulky selenolate ligands: X-ray crystal structure determination of [WH(SeC 6H 3Pr i2-2,6) 3(PMe 2Ph) 2

The complexes [WH(SeR) 3(L) (PMe 2Ph)] (R=C 6H 3Pr i 2-2,6 or C 6H 2Me 3-2,4,6; L=PMe 2Ph, pyridine and N-methylimidazole) have been prepared by reaction of [WH 6(PMe 2Ph) 3] or cis-[W(N 2) 2(PMe 2Ph) 4] with the selenol HSeR and characterized by FAB mass spectroscopy, 31P, 1H and 77Se NMR, IR and UV-Vis spectroscopies. A single crystal X-ray diffraction study of complex [WH(SeC 6H 3Pr i 2-2,6) 3(PMe 2Ph) 2] at 178 K reveals a distorted trigonal bipyramidal geometry of the WSe3P2 core with the hydride located along an SeP edge of the trigonal bipyramid; the hydride position was refined with a W-H distance of 1.51(6) A and an H-W-P angle of 53°. This small angle results in a large 2 J(H,P) coupling of 99 Hz. The bulky Se ligands adopt a 'two-up, one-down' arrangement of aryl substituents. The 2 J(SeP) values show a high degree of dependence on the P-M-Se angles or the P-M-Se-C dihedral angle. This may be useful for assigning geometries of selenolate complexes. Improved syntheses of the starting compounds [WH 6(PMe 2Ph) 3] and cis-[W(N 2) 2(PMe 2Ph) 4] are reported.

New hydrogen-containing zirconium clusters with phosphine ligands

Reaction of ZrCl 4 with 2 equiv. of HSnBu 3 followed by addition of phosphines yields hexazirconium cluster compounds [Zr 6Cl 14H 4(PR 3) 4] (2a: PR 3 = PMe 2Ph; 2b: PR 3 = PEt 2Pgh; 2c: PR 3 = PEt 3) and pentazirconium cluster compounds [Zr 5Cl 12H 4(PR 3) 5] (3a:PR 3 = PMe 2Ph; 3c; PR 3 = PEt 2). Treatment of compound 2a with Na/Hg in the presence of PMe 2Ph results in the formation [Zr 6Cl 12H 2(PMe 2Ph) 6] (4a). When the phosphine ligand is PEt 3, a similar reaction leads to the isolation of two new cluster compounds, [Zr 6Cl 12H 3(PEt 3) 6][ZrCl 5(PEt 3)] (5c) and [Zr 6Cl 13H 3(PEt 3) 5] (6c). In MeCN solution, compound 2a decomposes to form an ionic cluster compound, [HPMe 2Ph] 4[Zr 6Cl 18H 4] (7a). Cluster hydrogen atoms were observed by 1H NMR spectroscopy for all cluster compounds and by X-ray diffraction study for compound 3c where two hydrogen atoms ate μ 3-bridging and the other two edge-bridging. In compound 7a, there is evidence for the hydrogen atoms distributed near the centers of the one of the eight triangular faces of the Zr 6 octahedron. When ZrCl 4 reacts with 1 equiv. of HSnBu 3 followed by addition of PR 2Ph, only dinuclear compounds [Zr 2Cl 4(μ-Cl) 2(PR 2Ph) 4] (8a: R = Me; 8b; R = Et) are isolated. All compounds were characterized by X-ray crystallography and 1H NMR spectroscopy. Compound 2a∗d0.75CH 2Cl 2 crystallized in the monoclinic space group C2/ c with cell dimensions (−100°C) of a = 31.434(9), b = 15.255(6), c = 14.582(8) A ̊ , β = 106.08(2)°, V = 6719(9) A ̊ 3 and Z = 4. Compound 2b∗d2CH 2Cl 2 crystallized in the monoclinic space group P2 1/ c with cell dimensions (−60°C) of a = 11.310(1), b = 17.412(5), c = 17.807(2) A ̊ , β = 91.55(1)°, V = 3505(1) A ̊ 3 and Z = 2. Compound 2c∗d2C 6H 6 crystallized in the monoclinic space group P2 1/ n with cell dimensions (−150°C of a = 15.322(6), b = 12.186(3), c = 16.969(7) A ̊ , β = 91.09(2)°, V = 3117(2) A ̊ 3 and Z = 4. Coumpound 2c crystallized in the monoclinic space group C2/ c with cell dimensions (−150°C) of a = 26.128(9), b = 16.826(1), c = 13.411(4) A ̊ , β = 117.07(1)°, V = 5250(2) A ̊ 3 and Z = 4. Compounds 3c∗dC 6H 5CH 3 crystallized in the monoclinic space group C2/ c with cell dimensions (−75°C) of a = 48.06(1), b = 12.667(3), c = 22.829(5) A ̊ , β = 113.36(2)°, V = 12758(5) A ̊ 3 and Z = 8. Compound 4a crystallized in the triclinic space group P 1 with cell dimensions (−60°C) of a = 12.918(3), b = 15.493(2), c = 18.90(1) A ̊ , α = 90.31(6), β = 104.37(2), γ = 109.89(3)°, V = 3429(2) A ̊ 3 and Z = 2. Compound 5c∗d0.5C 6H 6 crystallized in the monoclinic space group P2/ c with cell dimensions (−60°C) of a = 23.707(6), b = 14.521(2), c = 25.109(3) A ̊ , β = 92.08(1)°, V = 8633(3) A ̊ 3 and Z = 4. Compound 6c∗dC 6H 6 crystallized in the orthorhombic space group Pna2 t with cell dimensions (−100°C) of a = 23.496(9), b = 23.973(2), c = 11.638(1) A ̊ , V = 6555(3) A ̊ 3 and Z = 4. Compound 7a∗d2MeCN crystallized in the triclinic space group P 1 with cell dimensions (20°C) of a = 12.881(2), b = 22.859(3), c = 12.208(2) A ̊ , α = 98.6614(1), β = 109.99(1), γ = 81.39(1)°, V = 3320.8(9) A ̊ 3 and Z = 2. Compounds 8b∗d0.67C 6H 5CH 3 crystallized in the rhombohedral spacve group r 3m with cell dimensions (−100°C) of a = 20.947(3), b = 20.947(3), c = 30.87(1) A ̊ , V = 11730(4) A ̊ 3 and Z = 6.