Tc Cl Research Articles

Synthesis, characterization and reactions of [Tc(NS)X 4] − complexes (XCl, Br, NCS)

The anions [Tc(NS)X 4] − (XCl, Br or NCS) can be prepared from the reaction of TcCl 6 2− and TcBr 6 2−, respectively, with trithiazyl chloride, (NSCI) 3. The equatorial ligands are kinetically labile and the complexes undergo ligand exchange reactions to form [Tc(NS)Cl n Br 4− n ] − mixed-ligand complexes ( n=1−3) or the isothiocyanate analogue [Tc(NS)(NCS) 4] −. The new compounds have been studied by EPR and the obtained parameters have been used to describe bonding properties. [Tc(NS)Cl 4] − and [Tc(NS)Br 4] − are instable in solution. Spontaneous decomposition results in nitridotechnetium(VI) complexes. The products have been characterized by EPR and X-ray diffraction.

Modulation of Tc–NX (X = O or S) bonds by π-acceptor ligands

Transfer of a sulfur atom from S2Cl2 to cis-[TcN(Cl)(phen)2]PF6(phen = 1,10-phenanthroline) yields cis-[Tc(NS)Cl(phen)2]PF6, which crystallizes in the triclinic space group, P(no. 2), with cell parameters a= 9.850(3), b= 16.293(3), c= 8.349(2)Å, α= 100.06(2), β= 93.84(3) and γ= 106.96(3)°. The Tc–NS bond length is 1.782(6)Å and the NS distance is 1.538(6)Å with a Tc–N–S bond angle of 170.0(4)°. Reaction of (NH4)2TcCl6 or NH4TcO4 with hydroxylamine hydrochloride in the presence of 1,10-phenanthroline yields cis-[Tc(NO)(NH3)(phen)2]2+. The compound cis-[Tc(NO)-(NH3)(phen)2][PF6]2·Me2CO crystallizes in the triclinic space group, P(no. 2), with a= 11.12(1), b= 14.25(6), c= 10.79(2)Å, α= 90.4(2), β= 107.9(1) and γ= 86.0(2)°. The Tc–NO bond length is 1.739(9)Å and the NO distance is 1.160(9)Å with a Tc–N–O bond angle of 171.9(8)°. Bond length and electrochemical data between series of complexes containing the [Tc–NX]2+(X = O or S) core indicate the effect of other π-acceptor ligands to be greater on thionitrosyl co-ordination.

Darstellung, Schwingungsspektren und Normalkoordinatenanalyse der Chloro-Bromo-Technetate(IV), [TcCl„Br6_n]2-, n = 0-6 / Preparation, Vibrational Spectra and Normal Coordinate Analysis of Chloro-Bromo-Technetates(IV), [TcCln Br6-n]2-, n = 0-6

The mixed chloro-bromo-technetates(IV), [TcClnBr6-n 2-, n = 1-5, have been separated for the first time by ion exchange chromatography on diethylaminoethyl-cellulose. Due to the stronger trans-effect of Br as compared to Cl, the ligand exchange reactions of [TcBr6 2- with HCl and of [TcCl6]2- with HBr proceed stereospecifically, to form either cis/fac- or trans/merspecies for n = 2, 3, 4, respectively. To avoid photoisomerization the compounds have to be handled in the absence of light. The IR and Raman spectra of the ten chloro-bromo-techne-tates(IV), including the pure geometrical isomers, have been recorded at low temperature (80 K) and completely assigned to structures of point groups Oh, D4h, C4v, C3v, and C2v, supported by normal coordinate analysis based on a general valence force field. Due to the different trans-influences Cl < Br in asymmetric Cl′—Tc— Br′ axes, the Tc— Br′ bonds are strengthened and the Tc—Cl′ bonds are weakened, as indicated by valence force constants, for Tc—Br′ on average 6% higher and for Tc—Cl′ 10% lower, as compared with the values calculated for symmetric Br—Tc—Br and CI—Tc—Cl axes, respectively.

The synthesis of a technetium(V) phenylimido complex from pertechnetate. The single crystal X-ray structure of [TcCl 3(NPh)(PPh 3) 2]·CH 2Cl 2

The reaction of (NH 4)[TcO 4] with triphenylphosphine and the organohydrazine N-acetyl, N′-phenylhydrazine (PhNHNHCOCH 3) in methanol with a minimal amount of HCl (aq) gives the neutral Tc(V) complex [Tc(NPh)Cl 3(PPh 3) 2] in very good yields. The IR spectrum of this complex displays a strong band in the 1090 cm −1 region which has tentatively been assigned to v(TcN). The (+)FAB mass spectrum does not show the peak associated with the neutral parent species [TcCl 3(NPh)(PPh 3) 2]. However, a prominent feature of 784 m/ z is associated with the fragment generated from the loss of a chloride ligand, giving the cationic species [TcCl 2(NPh)(PPh 3) 2] +. Other peaks present in the mass spectrum correspond to the fragments [TcCl 2(NPh)(PPh 3)] + of 522 m/ z and [TcCl(NPh)(PPh 3)]·H + of 488 m/ z. The diamagnetic Tc(V) complex displays a 1H NMR spectrum with the proton signals from the imido-phenyl group resolved from those of the phosphine-phenyl groups. The complex displays distorted octahedral molecular coordination geometry, with mutually trans triphenylphosphine ligands and equatorial phenylimido and chloride ligands. The technetium-nitrogen bond length is 1.704(4) Å with a technetium-nitrogen-carbon bond angle of 171.8(4)°, which reflects the sp hybridization of the phenylimido nitrogen atom. Bond lengths and angles involving the chloride and phosphine ligands are unexceptional for technetium in the +5 oxidation state. Crystal data for C 43H 37NP 2Cl 5Tc: triclinic space group P 1 , a=10.8651(9), b=12.2236(9), c=16.867(2) Å, a=71.998(7)°, β=74.078(7)°, γ=80.336(7)°, V=2040.2 Å 3, with D calc=1.455 g cm −3 to give Z=2. Structure solution based on 9334 reflections converged at R=0.054, R w=0.053, GOF=1.35. In an analogous reaction, [TcO 4] − reacts with benzoylhydrazine (PhCONHNH 2) and triphenylphosphine in methanol with HCl to give the Tc(V) nitrido complex [TcNCl 2(PPh 3) 2] in excellent yields.

Reaction products of ammonium pertechnetate(VII) with triphenylphosphine and crystal structures of mer-Tc(PPh3)2Cl3(DMF) •2PPh3 and NH2(CH3)2+DMAH+ [TcCl6]2−•PPh3O

The reaction of NH4TcO4 with PPh3 in DMF solution in the presence of HCl produces mer-Tciii(PPh3)2Cl3(DMF)•2PPh3 (1). When the reaction is done in acidic DMA, the yellow product isolated was identified as NH2(CH3)2+DMAH+ [TcCl6]2−•PPh3O (2). The dimethylammonium cation was produced from the reaction of the solvent (DMA) with aqueous HCl. The reaction of NH4TcO4 with PPh3 in acidic acetone solution produces yellow (PPh3H)2[TcCl6] (≈15% yield) and some orange crystals (≈65% yield) identified by X-ray diffraction as [Ph3P-C(CH3)2-CH2-CO-CH3]+ [Tc(PPh3)Cl5]−. The cation was produced from the reaction of acetone used as solvent with HCl and PPh3. The crystals of 1 are monoclinic with P21/m space group, a = 11.393(4), b = 24.993(11), c = 12.398(4) Å, β = 106.98(3)°, Z = 2. The structure was refined to R = 0.072 and wR = 0.058. The Tc—O bond distance is 2.115(12) Å while the Tc—P bond lengths are 2.496(5) and 2.499(5) Å and the Tc—Cl are 2.399(5) and 2.342(3) Å. The C atoms of the DMF ligand are disordered. The crystals of 2 are triclinic, [Formula: see text] space group with a = 8.627(5), b = 13.308(7), c = 14.401(9) Å, α = 97.62(5), β = 91.31(5), γ = 106.42(5)°, and Z = 2. The structure was refined to R = 0.060 and wR = 0.076. The proton on DMAH+ is hydrogen bonded to the oxygen of PPh3O with a distance [Formula: see text] Key words: technetium, DMF, triphenylphosphine, dimethylacetamide.

Structural and spectroscopic studies on mer-dichlorotris( dimethylphenyl-phosphine)(thionitrosyl)technetium(I), mer-[Tc(NS)Cl 2(Me 2PhP) 3

Structural and spectroscopic studies on mer-dichlorotris( dimethylphenyl-phosphine)(thionitrosyl)technetium(I), mer-[Tc(NS)Cl 2(Me 2PhP) 3

Preparation of the technetium(VI) aquanitrido complexes (NEt 4)[TcNX 4(OH 2)] (X= Cl or Br). Crystal structures of (NEt 4)[TcNBr 4(OH 2)] and Cs 2[TcNCl 5

Addition of NEt 4X to a conc. HX solution of [TcNX 4(OH 2)] − (X= Cl or Br) yields crystals of (NEt 4)[TcNX 4(OH 2)] (X=Cl ( 1) or Br ( 2)). Complex 2 crystallises in the orthorhombic space group Pnma with a = 11.366(1), b = 12.930(2), c = 11.540(1) Å and Z = 4. Refinement with 1434 data measured with Cu K α radiation converged with R = 0.047. The complex anion has distorted octahedral geometry with a water molecule trans to the nitrido ligand (TcN 1.599(9) and TcOH 2 2.443(7) Å). Crystals of Cs 2[TcNCl 5] ( 3) belong to the cubic space group Fm 3 m with a = 10.211(1) Å and Z = 4. The ligands of the complex anion are statistically disordered over six octahedral sites as required by the cubic space group. Refinement based on 78 data measured with Cu Kα radiation, and with a fixed TcN distance of 1.6 Å, converged with R = 0.034. In this model Tc is displaced 0.401(3) Å from the plane of the cis ligands towards the nitrido ligand with TcCl cis = 2.373(5), TcCl tras = 2.740(5) Å.

Bis(cyclopentadienyl)technetium(III)chlorid und Tris(cyclopentadienyl)technetium(III), neue metallorganische Verbindungen des dreiwertigen Technetiums

Abstract Technetium tetrachloride reacts with potassium cyclopentadienide in tetrahydrofuran to give the diamagnetic, air-stable (C 5 H 5 ) 2 TcCl ( 1 ). Single crystal X-ray diffraction analysis shows a short ring-metal distance of 187.7(5) pm, which is comparable with the corresponding distance in nickelocene, indicating high covalency. Reaction of the compound with KC 5 H 5 gives the red (C 5 H 5 ) 3 Tc ( 4 ), in which one cyclopentadienyl ring is σ-bonded. Mass spectroscopic investigations of the latter compound give evidence for the existence of (C 5 H 5 ) 4 Tc. The reactivity of (C 5 H 5 ) 2 TcCl is discussed.

Synthesis, characterization and x-ray molecular and crystal structure of Tc(NS)Cl 3(Me 2PhP)(Me 2PhPO)-a first example of mixed phosphine/phosphine oxide coordination

The reaction of TcNCl 2(Me 2PhP) 3 with excess S 2Cl 2 yields trichloro(dimethylphenylphosphine)- (dimethylphenylphosphine oxide)thionitrosyltechnetium(II), Tc(NS)Cl 3(Me 2PhP)(Me 2PhPO), whereas an equimolar reaction mixture yields dichlorotris (dimethylphenylphosphine)thionitrosyltechnetium- (I), Tc(NS)Cl 2(Me 2PhP) 3. Tc(NS)Cl 3(Me 2PhP)(Me 2 PhPO) (formula weight 543.74) crystallizes in the orthorhombic space group P2 12 12 1 with a= 10.513(1), b=14.274(2) and c=15.187(2) Å ( Z= 4). The phosphine oxide ligand is arranged in trans position to the linearly coordinated thionitrosyl group.

The chemistry of heteroallyl derivatives of technetium. Reactivity of [TcNCl2(PPh3)2] and [Tc(CO)3Cl(PPh3)] with thiazetidine ligands, crystal structures of [Tc(CO)2(PPh3)2{PhNC(OEt)S}] and [TcN(Cl)(PPh3)-{PhNC(OEt)S}

The complex [Tc(CO)3Cl(PPh3)] reacts with the sodium salt of PhNC(OEt)SH to give the thiazetidine complex [Tc(CO)2(PPh3)2{PhNC(OEt)S}](1). The complex [TcNCl2(PPh3)2] reacts with an excess of the neutral ligand to give [TcN(Cl)(PPh3){PhNC(OEt)S}](2). When the reaction is carried out in presence of the ligand salt the disubstituted complex [TcN{PhNC(OEt)S}2](3) is obtained. The crystal structures of (1) and (2) were determined by X-ray crystallography and refined to conventional R factors of 0.0295 and 0.0649 respectively. Compound (1) is monoclinic, space group P21, with a= 12.825(5), b= 16.713(5), c= 9.480(5)A, β= 94.29(3)°, and Z= 2. The technetium environment is distorted octahedral. Selected bond distances are: Tc–P(1) 2.423(1)A, Tc–P(2) 2.456(1), Tc–S 2.529(1), Tc–N 2.228(5), and Tc–C 1.89(1)A(mean). Compound (2) is triclinic, space group P, with a= 9.428(5), b= 10.237(5), c= 15.603(5)A, α= 89.29(3), β= 102.74(3), γ= 115.61 (3)°, and Z= 2. The environment of Tc is distorted square pyramidal with the nidrido N atom as apex. Selected bond distances are: Tc–N (nitrido) 1.615(7), Tc–N (ligand) 2.135(7), Tc–S 2.375(3), Tc–Cl 2.366(2), and Tc–P 2.429(2)A.

Synthesis and characterization of technetium-(IV) and -(III) complexes with bidentate Schiff bases. X-Ray molecular structure of chloro-(dimethylphenylphosphine)bis(N-phenylsalicylideneiminato)technetium(III)

The complexes [TcCl4(HL)2] and [TcCl3L(PPh3)][HL =N-methylsalicylideneimine or N-phenylsalicylideneimine (Hpsal)] of the long-lived isotope technetium-99 were synthesized from [TcCl4(PPh3)2], while the complexes [TcClL2(PMe2Ph)] were obtained through the reduction of the oxotechnetium(V) complexes [TcO(Cl)L2] with PMe2Ph. The crystal structure of the complex [TcCl(psal)2(PMe2Ph)] has been determined: a= 9.500(4), b= 10.596(4), c= 31.000(9)A, β= 95.59(5)°, monoclinic, space group P21/c, and Z= 4. The co-ordination around Tc is approximately octahedral with the two chelate ligands mutually orthogonal, one ligand bridging two adjacent positions in the plane normal to the Tc–P bond and the other in the plane normal to the Tc–Cl bond. The phosphorus atom of PMe2Ph is in a position trans to the aldimine nitrogen of one of the psal ligands, while the chlorine atom is trans to the nitrogen atom of the second psal, leaving the two phenolic oxygens in trans positions to each other.

Studies of technetium complexes. Part 6. The preparation, characterisation, and electron spin resonance spectra of salts of tetrachloro- and tetrabromo-nitridotechnetate(VI): crystal structure of tetraphenylarsonium tetrachloronitridotechnetate(VI)

The air-stable compounds R[TcNCl4] and R[TcNBr4](R =[AsPh4]+ or [NBun4]+) have been prepared by the reaction of [NH4][TcO4] with NaN3 in the presence of concentrated HCl or of HBr. The e.s.r. spectra of [TcNCl4]– and [TcNBr4]– are typical of ions with a 4d1 electronic configuration and the unpaired electron in an orbital with substantial 4dxy character. The crystal structure of [AsPh4][TcNCl4] has been determined by single-crystal X-ray diffraction methods at 21 °C. Crystals are tetragonal, space group P4/n, with a= 12.707(2), c= 7.793(1)A, and Z= 2. Full-matrix least-squares refinement gave a final R value of 0.031 for 1 079 independent reflections. The compound is isostructural with the series [AsPh4][MNCl4](M = Mo, W, Re, Ru, or Os) and with [AsPh4][MOCl4](M = Mo or Re). The [TcNCl4]– anion in [AsPh4][TcNCl4] possesses C4v symmetry with Cl–Tc–Cl bond angles of 86.95(1) and 153.33(6)° and NTc–Cl bond angles of 103.34(3)°. The TcN bond distance is 1.581 (5)A and the Tc–Cl distances are 2.3220(9)A.

Synthesis and characterization of technetium(V) oxo-complexes with quadridentate Schiff-base ligands: X-ray structures of µ-oxo-bis-{oxo[N,N′-propane-1,3-diylbis(salicylideneiminato)]technetium(V)} and chloro-oxo[N,N′-propane-1,3-diylbis(salicylideneiminato)]-technetium(V)

The reactions of quadridentate Schiff-base ligands derived from salicylaldehyde and diamines with [TcOCl4]– have been investigated. The complexes [NBu4][TcOCl3(Hsalpd)], [NBu4][TcOCl3(Hsalbd)], [{TcO(salpd)}2O], [TcOCl(salpd)], and [TcOCl(salbd)][salpd =N,N′-propane-1,3-diylbis-(salicylideneiminate), salbd =N,N′-butane-1,4-diylbis(salicylideneiminate)] were isolated from the reaction mixture in ethanol. The complexes have been characterized by elemental analysis and by i.r. spectroscopy. The crystal structures of [{TcO(salpd)}2]O (1) and [TcOCl(salpd)](2) have been determined from three-dimensional X-ray data: (1), monoclinic, space group P21/c, a= 15.041 (2), b= 12.630(3), c= 16.522(4)A, β= 95.35(3)° and Z= 4; (2), orthorhombic, space group Pn21a, a= 12.010(4), b= 11.702(4), c= 11.625(6)A, and Z= 4. The structures have been solved by Patterson and Fourier methods and refined by least-squares methods to R 0.059 for (1) and 0.076 for (2). The ‘dimeric’ structure of (1) consists of two crystallographically independent and chemically well separated TcO(salpd) moieties bridged by an oxygen atom with the bridging Tc–O–Tc angle symmetrically imposed at 180°. A novel feature is the presence of the almost linear OTc–O–TcO group. The technetium atoms have octahedral co-ordination, with the equatorial plane formed by the N2O2 donor set, and the chelate ligand, as a whole, is very nearly planar. The structure of (2) consists of discrete molecules of [TcOCl(salpd)] with a pseudo-octahedral co-ordination around technetium. The salpd ligand occupies the four equatorial positions, whereas the Cl and the oxygen are trans to each other in axial positions. The two salicylaldimine groups are bent in an ‘umbrella shape’. Bond distances (A) in the ‘inner core’: (1), TcO 1.68, Tc–O(bridging) 1.90, Tc–O 2.01, and Tc–N 2.12 A; (2), TcO 1.66, Tc–O 1.98, Tc–N 2.12, Tc–Cl 2.44 A, estimated standard deviations being 0.01 A for (1) and 0.02 A for (2).

ChemInform Abstract: REACTIONS OF PERTECHNETATE ANION WITH TRIPHENYLPHOSPHINE. MOLECULAR STRUCTURE (AT ‐100°C) OF (1,1‐DIMETHYL‐3‐OXOBUTYL)TRIPHENYLPHOSPHONIUM PENTACHLORO(TRIPHENYLPHOSPHINE)TECHNETATE(IV)

AbstractDas Ion [TcO4]′ reagiert mit PPh3 im Verhältnis 1 :7 und HCl in stöchiometrischem Verhältnis bzw. mit PPh3 im Verhältnis 1 : l0 und HCl (1:100) in Me, CO bei Raumtemp. zu den Komplexen (I) bzw. (II).

Reactions of pertechnetate anion with triphenylphosphine. Molecular structure (at –100 °C) of (1,1-dimethyl-3-oxobutyl)triphenylphosphonium pentachloro(triphenylphosphine)technetate(IV)

The reactions of the [TcO4]– anion with PPh3 in various concentrations of HCl are reported. [TcCl4(PPh3)2], [TcCl5(PPh3)]–, and [TcCl6]2– were obtained and the anionic complexes were isolated with cations such as [PPh3H]+, [AsPh4]+, or [Ph3PC(Me)2CH2COMe]+. The crystal structure of the title complex was determined at –100 °C from 1 761 independent reflections and refined to R= 0.065. Crystals are monoclinic, space group P21/n, a= 21.909(4), b= 18.963(4), c= 9.896(3)A, β= 103.05(5)°, and Z= 4. The structure consists of well separated units of octahedral [TcCl5(PPh3)]– anions, and tetrahedral phosphonium cations, in which the phenyl groups are in a ′ propeller ′ configuration around P. Selected bond distances and angles are Tc–Cl (mean) 2.34(1), Tc–P 2.57(1)A, Cl–Tc–Cl (mean) 90.7(4), Cl–Tc–P 88.7(4)°.

ChemInform Abstract: PREPARATION AND MOLECULAR STRUCTURE OF TRANS‐CHLOROBIS(PENTANE‐2,4‐DIONATO)(TRIPHENYLPHOSPHINE)TECHNETIUM(III)

The title complex trans-[Tc(pd)2(PPh3)Cl], prepared by reaction of pentane-2,4-dione(pd) with trans-[Tc(PPh3)2Cl4], crystallises in the centrosymmetric space group P with a= 13.152(8), b= 15.042(10), c= 15.532(13)A, α= 112.26(11), β= 91.01(7), γ= 104.70(9)°, and Z= 4. Intensity measurements have been made with Mo-Kα radiation for the 6 601 independent reflections having 2θ⩽ 44° utilising the θ—2θ scan technique on a diffractometer. The structure has been solved by using the heavy-atom technique and has been refined using full-matrix least-squares procedures to a final R value of 0.063 using 4 950 independent reflections having I > 3σ(I). There are two crystallographically independent molecules which differ chiefly in the folding angles of the pd ligands about the O ⋯ O ‘bite’ axis. The octahedral co-ordination polyhedron is tetragonally elongated and approximates idealised D4h symmetry. The four ‘short’ Tc–O bonds have an average length of 2.01(1)A, while the two ‘long’trans Tc–Cl and Tc–P have lengths of 2.42(1) and 2.46(1)A, respectively. The bonding scheme and trans conformation are discussed in terms of the angular-overlap molecular-orbital model.

Preparation and molecular structure of trans-chlorobis(pentane-2,4-dionato)(triphenylphosphine)technetium(III)

The title complex trans-[Tc(pd)2(PPh3)Cl], prepared by reaction of pentane-2,4-dione(pd) with trans-[Tc(PPh3)2Cl4], crystallises in the centrosymmetric space group P with a= 13.152(8), b= 15.042(10), c= 15.532(13)A, α= 112.26(11), β= 91.01(7), γ= 104.70(9)°, and Z= 4. Intensity measurements have been made with Mo-Kα radiation for the 6 601 independent reflections having 2θ⩽ 44° utilising the θ—2θ scan technique on a diffractometer. The structure has been solved by using the heavy-atom technique and has been refined using full-matrix least-squares procedures to a final R value of 0.063 using 4 950 independent reflections having I > 3σ(I). There are two crystallographically independent molecules which differ chiefly in the folding angles of the pd ligands about the O ⋯ O ‘bite’ axis. The octahedral co-ordination polyhedron is tetragonally elongated and approximates idealised D4h symmetry. The four ‘short’ Tc–O bonds have an average length of 2.01(1)A, while the two ‘long’trans Tc–Cl and Tc–P have lengths of 2.42(1) and 2.46(1)A, respectively. The bonding scheme and trans conformation are discussed in terms of the angular-overlap molecular-orbital model.

ChemInform Abstract: PREPARATION AND CRYSTAL AND MOLECULAR STRUCTURE OF MER‐TRICHLOROTRIS(DIMETHYLPHENYLPHOSPHINE)TECHNETIUM(III)

Chemischer InformationsdienstVolume 7, Issue 14 Organoelement Compounds ChemInform Abstract: PREPARATION AND CRYSTAL AND MOLECULAR STRUCTURE OF MER-TRICHLOROTRIS(DIMETHYLPHENYLPHOSPHINE)TECHNETIUM(III) GIULIANO BANDOLI, GIULIANO BANDOLISearch for more papers by this authorDORE A. CLEMENTE, DORE A. CLEMENTESearch for more papers by this authorULDERICO MAZZI, ULDERICO MAZZISearch for more papers by this author GIULIANO BANDOLI, GIULIANO BANDOLISearch for more papers by this authorDORE A. CLEMENTE, DORE A. CLEMENTESearch for more papers by this authorULDERICO MAZZI, ULDERICO MAZZISearch for more papers by this author First published: April 6, 1976 https://doi.org/10.1002/chin.197614296Read the full textAboutPDF 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 No abstract is available for this article. Volume7, Issue14April 6, 1976 RelatedInformation

Preparation and crystal and molecular structure of mer-trichlorotris(dimethylphenylphosphine)technetium(III)

The crystal and molecular structure of the title compound has been determined from single-crystal X-ray diffractometer data by Fourier methods and refined by anisotropic block-diagonal least-squares to R 0.054 for 4 065 independent observed reflections. Crystals are monoclinic, space group P21/n, with cell parameters a= 10.935(9), b= 39.191(11), c= 13.738(7)A, β= 107.33(7)°, and Z= 8. The two crystallographically independent molecules are stereochemically equivalent (there is only a small difference in the orientation of a benzene ring) and the metal atom has a somewhat distorted octahedral co-ordination, with two pairs of like ligands mutually trans. Technetium–ligand bond distances are: Tc–Cl (trans to P) 2.46(1), Tc–Cl (trans to Cl) both 2.33(1), Tc–P (trans to Cl) 2.42(1) and Tc–P (trans to P) both 2.47(1)A. The noticeble trans-influence of the phosphine ligands on Tc–Cl bonds is discussed.