共查询到20条相似文献，搜索用时 125 毫秒
1.
Synthesis and Spectroscopic Characterization of [Rh(SeCN)6]3– and trans ‐[Rh(CN)2(SeCN)4]3–, Crystal Structure of (Me4N)3[Rh(SeCN)6] Treatment of RhCl3 with KSeCN in acetone yields a mixture of selenocyanato‐rhodates(III), from which [Rh(SeCN)6]3– and trans‐[Rh(CN)2(SeCN)4]3– have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of (Me4N)3[Rh(SeCN)6] (trigonal, space group R3, a = 14.997(2), c = 24.437(3) Å, Z = 6) reveals, that the compound crystallizes isotypically to (Me4N)3[Ir(SCN)6]. The exclusively via Se coordinated selenocyanato ligands are bonded with the average Rh–Se distance of 2.490 Å and the Rh–Se–C angle of 104.6°. In the low temperature IR and Raman spectra the metal ligand stretching modes ν(RhSe) of (n‐Bu4N)3[Rh(SeCN)6] ( 1 ) and trans‐(n‐Bu4N)3[Rh(CN)2(SeCN)4] ( 2 ) are in the range of 170–250 cm–1. In 2 νas(CRhC) is observed at 479 cm–1. The vibrational spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(RhSe) = 1.08 ( 1 ), 1.10 ( 2 ) and fd(RhC) = 3.14 mdyn/Å ( 2 ). fd(RhS) = 1.32 mdyn/Å is determined for [Rh(SCN)6]3–, which has not been calculated so far. The 103Rh NMR resonances are 2287 ( 1 ), 1680 ppm ( 2 ) and the 77Se NMR resonances are –32.7 ( 1 ) and –110.7 ppm ( 2 ). The Rh–C bonding of the cyano ligand in 2 is confirmed by a dublett in the 13C NMR spectrum at 136.3 ppm. 相似文献
2.
Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N3)4(ECN)2]2–, E = S, Se By oxidative addition to (n‐Bu4N)2[Pt(N3)4] with dirhodane in dichloromethane trans‐(n‐Bu4N)2[Pt(N3)4(SCN)2] and by ligand exchange of trans(n‐Bu4N)2[Pt(N3)4I2] with Pb(SeCN)2 trans‐(n‐Bu4N)2[Pt(N3)4(SeCN)2] are formed. X‐ray structure determinations on single crystals of trans‐(Ph4P)2[Pt(N3)4(SCN)2] (triclinic, space group P 1, a = 10.309(3), b = 11.228(2), c = 11.967(2) Å, α = 87.267(13), β = 75.809(16), γ = 65.312(17)°, Z = 1) and trans‐(Ph4P)2[Pt(N3)4(SeCN)2] (triclinic, space group P 1, a = 9.1620(10), b = 10.8520(10), c = 12.455(2) Å, α = 90.817(10), β = 102.172(10), γ = 92.994(9)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–S = 2.337, Pt–Se = 2.490 and Pt–N = 2.083 (S), 2.053 Å (Se). The approximate linear Azidoligands with Nα–Nβ–Nγ‐angles = 172,1–175,0° are bonded with Pt–Nα–Nβ‐angles = 116,7–120,5°. In the vibrational spectra the platinum chalcogen stretching vibrations of trans‐(n‐Bu4N)2[Pt(N3)4(ECN)2] are observed at 296 (E = S) and in the range of 186–203 cm–1 (Se). The platinum azide stretching modes of the complex salts are in the range of 402–425 cm–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtS) = 1.64, fd(PtSe) = 1.36, fd(PtNα) = 2.33 (S), 2.40 (Se) and fd(NαNβ, NβNγ) = 12.43 (S), 12.40 mdyn/Å (Se). 相似文献
3.
Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N3)4X2]2–, X = Cl, Br, I By oxidative addition to (n‐Bu4N)2[Pt(N3)4] with the elemental halogens in dichloromethane trans‐(n‐Bu4N)2[Pt(N3)4X2], X = Cl, Br, I are formed. X‐ray structure determinations on single crystals of trans‐(Ph4P)2[Pt(N3)4Cl2] (triclinic, space group P1, a = 10.352(1), b = 10.438(2), c = 11.890(2) Å, α = 91.808(12), β = 100.676(12), γ = 113.980(10)°, Z = 1), trans‐(Ph4P)2[Pt(N3)4Br2] (triclinic, space group P1, a = 10.336(1), b = 10.536(1), c = 12.119(2) Å, α = 91.762(12), β = 101.135(12), γ = 112.867(10)°, Z = 1) and trans‐(Ph4P)2[Pt(N3)4I2] (triclinic, space group P1, a = 10.186(2), b = 10.506(2), c = 12.219(2) Å, α = 91.847(16), β = 101.385(14), γ = 111.965(18)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–Cl = 2.324, Pt–Br = 2.472, Pt–I = 2.619 and Pt–N = 2.052–2.122 Å. The approximate linear Azidoligands with Nα–Nβ–Nγ‐angles = 172.1–176.8° are bonded with Pt–Nα–Nβ‐angles = 116.2–121.9°. In the vibrational spectra the platinum halogen stretching vibrations of trans‐(n‐Bu4N)2[Pt(N3)4X2] are observed in the range of 327–337 (X = Cl), at 202 (Br) and in the range of 145–165 cm–1 (I), respectively. The platinum azide stretching modes of the three complex salts are in the range of 401–421 cm–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtCl) = 1.90, fd(PtBr) = 1.64, fd(PtI) = 1.22, fd(PtNα) = 2.20–2.27 and fd(NαNβ, NβNγ) = 12.44 mdyn/Å. 相似文献
4.
Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Tetrahalogeno‐bis‐Pyridine‐Osmium(III) Complexes cis ‐( n ‐Bu4N)[OsCl4Py2] and trans ‐( n ‐Bu4N)[OsX4Py2], X = Cl, Br By reaction of (n‐Bu4N)2[OsX6], X = Cl, Br, with pyridine and (n‐Bu4N)[BH4] tetrahalogeno‐bis‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of cis‐(n‐Bu4N)[OsCl4Py2] ( 1 ) (triclinic, space group P1, a = 9.4047(9), b = 10.8424(18), c = 17.007(2) Å, α = 71.833(2), β = 81.249(10), γ = 67.209(12)°, Z = 2), trans‐(n‐Bu4N)[OsCl4Py2] ( 2 ) (orthorhombic, space group P212121, a = 8.7709(12), b = 20.551(4), c = 17.174(4) Å, Z = 4) and trans‐(n‐Bu4N)[OsBr4Py2] ( 3 ) (triclinic, space group P1, a = 9.132(3), b = 12.053(3), c = 15.398(2) Å, α = 95.551(18), β = 94.12(2), γ = 106.529(19)°, Z = 2). Based on the molecular parameters of the X‐ray structure determinations and assuming C2 point symmetry for the anion of 1 and D2h point symmetry for the anions of 2 and 3 the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants of 1 are in the Cl–Os–Cl axis fd(OsCl) = 1.58, in the asymmetrically coordinated N′–Os–Cl · axes fd(OsCl · ) = 1.45, fd(OsN′) = 2.48, of 2 fd(OsCl) = 1.62, fd(OsN) = 2.42 and of 3 fd(OsBr) = 1.39 and fd(OsN) = 2.34 mdyn/Å. 相似文献
5.
Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of trans ‐( n ‐Bu4N)4[Pt(ECN)2(ox)2], E = S, Se By reaction of (n‐Bu4N)2[Pt(ox)2] with (SCN)2 and (SeCN)2 in dichloromethane trans‐(n‐Bu4N)2[Pt(SCN)2(ox)2] ( 1 ) und trans‐(n‐Bu4N)2[Pt(SeCN)2(ox)2] ( 2 ) are formed. The crystal structures of 1 (triclinic, space group P1, a = 10.219(2), b = 11.329(2), c = 12.010(3) Å, α = 114.108(15), β = 104.797(20), γ = 102.232(20)°, Z = 1) and 2 (triclinic, space group P1, a = 10.288(1), b = 11.332(1), c = 12.048(1) Å, α = 114.391(9), β = 103.071(10), γ = 102.466(12)°, Z = 1) reveal, that the compounds crystallize isotypically with centrosymmetric complex anions. The bond lengths are Pt–S = 2.357, Pt–Se = 2.480 and Pt–O = 2.011 ( 1 ) und 2.006 Å ( 2 ). The oxalato ligands are nearly plane with O–C–C–O torsion angles of 1.7–3.6°. The via S or Se coordinated linear groups are inclined between both oxalato ligands with Pt–E–C angles of 100.4 (E = S) and 97.4° (Se). In the vibrational spectra the PtE stretching vibrations are observed at 299–314 ( 1 ) and 189–200 cm–1 ( 2 ). The PtO stretching vibrations are coupled with internal vibrations of the oxalato ligands and appear in the range of 400–800 cm–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtS) = 1.75, fd(PtSe) = 1.35 and fd(PtO) = 2.77 mdyn/Å. The NMR shifts are δ(195Pt) = 5435.2 ( 1 ), 5373.7 ( 2 ) and δ(77Se) = 353.2 ppm with the coupling constant 1J(SePt) = 37.4 Hz. 相似文献
6.
Crystal Structures, Spectroscopic Analysis, and Normal Coordinate Analysis of ( n ‐Bu4N)2[M(ECN)4] (M = Pd, Pt; E = S, Se) The reaction of (NH4)2[PdCl4] or K2[PtCl4] with KSCN or KSeCN in aqueous solutions yields the complex anions [Pd(SCN)4]2–, [Pt(SCN)4]2– and [Pt(SeCN)4]2–, which are converted into (n‐Bu4N) salts with (n‐Bu4N)HSO4. (n‐Bu4N)2[Pd(SeCN)4] is formed by treatment of (n‐Bu4N)2[PdCl4] with (n‐Bu4N)SeCN in acetone. X‐ray structure determinations on single crystals of (n‐Bu4N)2[Pd(SCN)4] (monoclinic, space group P21/n, a = 13.088(3), b = 12.481(2), c = 13.574(3) Å, β = 91.494(15)°, Z = 2), (n‐Bu4N)2[Pd(SeCN)4] (monoclinic, space group P21/n, a = 13.171(2), b = 12.644(2), c = 13.560(2) Å, β = 91.430(11)°, Z = 2) and (n‐Bu4N)2[Pt(SeCN)4] (monoclinic, space group P21/n, a = 13.167(2), b = 12.641(1), c = 13.563(2) Å, β = 91.516(18)°, Z = 2) reveal, that the compounds crystallize isotypically and the complex anions are centrosymmetric and approximate planar. In the Raman spectra the metal ligand stretching modes of (n‐Bu4N)2[Pd(SCN)4] ( 1 ) and (n‐Bu4N)2[Pt(SCN)4] ( 3 ) are observed in the range of 260–303 cm–1 and of (n‐Bu4N)2[Pd(SeCN)4] ( 2 ) and (n‐Bu4N)2[Pt(SeCN)4] ( 4 ) in the range of 171–195 cm–1. The IR and Raman spectra are assigned by normal coordinate analysis using the molecular parameters of the X‐ray determination. The valence force constants are fd(PdS) = 1.17, fd(PdSe) = 1.17, fd(PtS) = 1.44 and fd(PtSe) = 1.42 mdyn/Å. The 77Se NMR resonances are 23 for 2 , –3 for 4 and the 195Pt NMR resonances 549 for 3 and 130 ppm for 4 . 相似文献
7.
Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of cis‐ and trans‐(n‐Bu4N)2[PtF2(ox)2] and (n‐Bu4N)2[PtF4(ox)] By treatment of trans‐(n‐Bu4N)2[PtCl2(ox)2] and (n‐Bu4N)2[PtCl4(ox)] with XeF2 in propylene carbonate cis‐ and trans‐(n‐Bu4N)2[PtF2(ox)2] ( 1 , 2 ) and (n‐Bu4N)2[PtF4(ox)] ( 3 ) are formed which have been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structure of trans(n‐Bu4N)2[PtF2(ox)2] ( 2 ) (tetragonal, space group P42/n, a = 15.5489(9), b = 15.5489(9), c = 17.835(1)Å, Z = 4) und Cs2[PtF4(ox)] ( 3 ) (monoclinic, space group C2/m, a = 14.5261(7), b = 6.2719(4), c = 9.6966(9)Å, β = 90.216(8)°, Z = 4) reveal complex anions with nearly D2h and C2v point symmetry. The average bond lengths in the symmetrical coordinated axes are Pt—F = 1.93 ( 2 , 3 ) and Pt—O = 1.987 ( 2 ) and in the F•—Pt—O′‐axes Pt—F• = 1.957 and Pt—O′ = 1.977Å ( 3 ). The oxalato ligands are nearly planar with a maximum displacement of the ring atoms of 0.05 ( 2 ) und 0.01Å ( 3 ) to the calculated best planes. In the vibrational spectra the symmetric and antisymmetric PtF stretching vibrations are observed at 583 and 586 ( 2 ) and 576 and 568 cm—1 ( 3 ). The PtF• modes appear at 565 and 562 ( 1 ) and 560 cm—1 ( 3 ). The PtO and PtO′ stretching vibrations are coupled with internal modes of the oxalato ligands and appear in the range of 400—800 cm—1. Based on the molecular parameters of the X‐ray determinations ( 2 , 3 ) and estimated data ( 1 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtF) = 3.55 ( 2 ) and 3.38 ( 3 ), fd(PtF•) = 3.23 ( 1 ) and 3.20 ( 3 ), fd(PtO) = 2.65 ( 1 ) and 2.84 ( 2 ) and fd(PtO′) = 2.97 ( 1 ) and 3.00 mdyn/Å ( 3 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(195Pt) = 8485 ( 1 ), 8597 ( 2 ) and 10048 ppm ( 3 ), δ(19F) = —350 ( 2 ) and —352 ( 3 ) and δ(19F•) = —323 ( 1 ) and —326 ppm ( 3 ) with the coupling constants 1J(PtF) = 1784 ( 2 ) and 1864 ( 3 ) and 1J(PtF•) = 1525 ( 1 ) and 1638 Hz ( 3 ). 相似文献
8.
Preparation, Crystal Structure, and Normal Coordinate Analysis of Linkage Isomeric Pentachloroiodoselenocyanatoosmates(IV). Crystal Structure of trans‐(PPh4)2[OsCl4I(NCSe)] By treatment of the solution of (n‐Bu4N)2[OsCl5I] in dichloromethane with suspended Pb(SeCN)2 the linkage isomers trans‐(n‐Bu4N)2[OsCl4I(NCSe)] ( 1 ) and trans‐(n‐Bu4N)2[OsCl4I(SeCN)] ( 2 ) are formed, which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐Ray structure determination on a single crystal of trans‐(PPh4)2[OsCl4I(NCSe)] (triclinic, space group P1¯, a = 10.8950(13), b = 11.076(2), c = 20.980(2)Å, α = 96.940(10), β = 98.747(9), γ = 104.419(11)°, Z = 2) reveals, that the nearly linear selenocyanate group in trans position to the iodine atom is coordinated with the Os‐N‐C angle of 171.1°. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra of both linkage isomers are assigned by normal coordinate analysis. The valence force constants are fd(OsN) = 1.70 und fd(OsSe) = 1.15 mdyn/Å. 相似文献
9.
Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (Ph4P)2[OsN(N3)5] and 15N NMR Chemical Shifts of Nitridoosmates(VI, VIII) The treatment of (Ph4P)[OsNCl4] with NaN3 yields (Ph4P)2[OsN(N3)5], which crystal structure has been determined by single crystal X‐ray diffraction analysis (monoclinic, space group P 21/a, a = 20.484(6), b = 11.168(1), c = 20.666(4) Å, β = 97.35(3)°, Z = 4). The IR and Raman vibrations were assigned by a normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(Os≡N) = 8.52, fd(Os–Nα) = 1.99, fd(Nα–Nβ) = 12.42, fd(Nβ–Nγ) = 12.73 and for the azido ligand in trans‐position to the nitrido group fd(Os–Nα · ) = 1.84, fd(Nα · –Nβ · ) = 11.91, fd(Nβ · –Nγ · ) = 12.18 mdyn/Å. The 15N NMR spectra of various nitridoosmates reveal the chemical shifts δ(15N) for K[OsO315N] = 387.6, K2[Os15NCl5] = 446.7, (Ph4P)[Os15NCl4] = 352.9, [(n‐C6H13)4N]2[Os15N(N3)5] = 307.3 and for [(n‐Pr)4N]2[Os15N(15NCO)5] = 483,7 (Os≡N), –417,7 (OsNCOeq) und –392,8 ppm (OsNCOax). 相似文献
10.
Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of the Linkage Isomeric Chlororhodanoiridates(III) trans-[IrCl2(SCN)4]3? and trans-[IrCl2(NCS)(SCN)3]3? By treatment of Na2[IrCl6] with NaSCN in 2N HCl the linkage isomers trans-[IrCl2(SCN)4]3? and trans-[IrCl2(NCS)(SCN)3]3? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-ray structure determinations on single crystals of trans-(n-Bu4N)3[IrCl2(SCN)4] ( 1 ) (monoclinic, space group P21/a, a = 18.009(4), b = 15.176(3), c = 23.451(4) Å, β = 93.97(2)°, Z = 4) and trans-(Me4N)3[IrCl2(NCS)(SCN)3] ( 2 ) (monoclinic, space group P21/a, a = 17.146(5), b = 9.583(5), c = 18.516(5) Å, β = 109.227(5)°, Z = 4) reveal the complete ordering of the complex anions. The via S or N coordinated thiocyanate groups are bonded with Ir? S? C angles of 105.7–109.7° and the Ir? N? C angle of 171.4°. The torsion angles Cl? Ir? S? C and N? Ir? S? C are 3.6–53.0°. The IR and Raman spectra of ( 1 ) are assigned by normal coordinate analysis using the molecular parameters of the X-ray determination. The valence force constants are fd(IrS) = 1.52 and fd(IrCl) = 1.72 mdyn/Å. 相似文献
11.
Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of cis -(Et4N)[OsF2Cl4] and trans -(Ph4P)[OsF2Cl4] By oxidation of the pure fluorochloroosmates(IV) with KBrF4 or PbO2/trifluoracetic acid in dichloromethane the mixed pentavalent complex anions cis-[OsF2Cl4]– and trans-[OsF2Cl4]– are formed. X-ray structure determinations on single crystals have been performed of cis-(Et4N) · [OsF2Cl4] ( 1 ) (monoclinic, space group P21/n, a = 7.519(2), b = 17.648(2), c = 11.942(4) Å, β = 105.98(2)°, Z = 4) and trans-(Ph4P)[OsF2Cl4] ( 2 ) (tetragonal, space group P4/n, a = 12.677(2), c = 7.743(1) Å, Z = 2). Based on the molecular parameters of the X-ray determinations and assuming C2v point symmetry for the anion of 1 and D4h point symmetry for the anion of 2 the IR and Raman spectra have been assigned by normal coordinate analysis. Due to the stronger trans influence of chlorine as compared with fluorine for F · –Os–Cl′ axes significally different valence force constants are observed in comparison with symmetrically coordinated axes: fd(OsF · ) = 3.35, fd(OsF) = 3.73, fd(OsCl′) = 2.05 and fd(OsCl) with 1.98 and 2.00 mdyn/Å. 相似文献
12.
Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of trans-(PNP)[TcCl4(Py)2] and trans-(PNP)[TcBr4(Py)2] By reaction of (PNP)2[TcX6] with pyridine in the presence of [BH4]? (PNP)[TcX4(Py)2], X = Cl, Br, are formed. X-ray structure determinations on single crystals of these isotypic TcIII complexes (monoclinic, space group P21/n, Z = 2, for X = Cl: a = 13.676(4), b = 9.102(3), c = 17.144(2) Å, β = 91.159(1)°; for X = Br: a = 13.972(2), b = 9.146(3), c = 17.285(4) Å, β = 90.789(2)°) result in the averaged bond distances Tc? Cl: 2.386, Tc? Br: 2.519, Tc? N: 2.132(3) (X = Cl) and 2.143(4) Å (X = Br). The two pyridine rings are coplanar and vertical to the X? Tc? X-axes, forming angles of 42.28° (X = Cl) and 43.11° (X = Br). Using the molecular parameters of the X-ray structure determination and assuming D2h point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis based on a modified valence force field. Good agreement between observed and calculated frequencies is obtained with the valence force constants fd(TcCl) = 1.45, fd(TcBr) = 1.035, fd(TcN) = 1.37 (X = Cl) and 1.45 mdyn/ Å (X = Br), respectively. 相似文献
13.
A Contribution to Rhenium(II)‐, Osmium(II)‐, and Technetium(II)‐Thionitrosyl‐Complexes: Preparation, Structures, and EPR‐Spectra The reaction of [ReVINCl4]— and [OsVINCl4]— with S2Cl2 leads to the formation of the thionitrosyl complexes [MII(NS)Cl4]— (M = Re, Os) which could not be isolated as pure compounds. Addition of pyridine to the reaction mixture results in the formation of the stable compounds trans‐(Ph4P)[OsII(NS)Cl4py], trans‐(Hpy)[OsII(NS)Cl4py], trans‐(Ph4P)[ReII(NS)Cl4py], and cis‐(Ph4P)[ReII(NS)Cl4py]. The crystal structure analyses show for trans‐(Ph4P)[OsII(NS)Cl4py] (monoclinic, P21/n, a = 12.430(3)Å, b = 18.320(4)Å, c = 15.000(3)Å, β = 114.20(3)°, Z = 4), trans‐(Hpy)[OsII(NS)Cl4py] (monoclinic, P21/n, a = 7.689(1)Å, b = 10.202(2)Å, c = 20.485(5)Å, β = 92.878(4)°, Z = 4), trans‐(Ph4P)[ReII(NS)Cl4py] (triclinic, P1¯, a = 9.331(5)Å, b = 12.068(5)Å, c = 15.411(5)Å, α = 105.25(1)°, β = 90.23(1)°, γ = 91.62(1)°, Z = 2), and cis‐(Ph4P)[ReII(NS)Cl4py] (monoclinic, P21/c, a = 10.361(1)Å, b = 16.091(2)Å, c = 17.835(2)Å, β = 90.524(2)°, Z = 4) M‐N‐S angles in the range 168‐175°. This indicates a nearly linear coordination of the NS ligand. The metal atom is octahedrally coordinated in all cases. The rhenium(II) thionitrosyl complexes (5d5 “low‐spin” configuration, S = 1/2) are studied by EPR in the temperature range 295 > T > 130 K. In addition to the detection of the complexes formed during the reaction of [ReVINCl4]— with S2Cl2 EPR investigations on diamagnetically diluted powders and single crystals of the system (Ph4P)[ReII/OsII(NS)Cl4py] are reported. The 185, 187Re hyperfine parameters are used to get information about the spin‐density distribution of the unpaired electron in the complexes under study. [TcVINCl4]— reacts with S2Cl2 under formation of [TcII(NS)Cl4]— which is not stable and decomposes under S8 elimination and rebuilding of [TcVINCl4]— as found by EPR monitoring of the reaction. 相似文献
14.
Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of cis‐(n‐Bu4N)2[Pt(ECN)2(ox)2], E = S, Se By exposure of trans‐(n‐Bu4N)2[Pt(ECN)2(ox)2], E = S and Se, in dichloromethane cis‐(n‐Bu4N)2[Pt(SCN)2(ox)2] ( 1 ) and cis‐(n‐Bu4N)2[Pt(SeCN)2(ox)2] ( 2 ) are formed. The crystal structure of 1 (triclinic, space group P1¯, a = 10.789(1), b = 11.906(1), c = 18.580(1)Å, α = 85.619(10), β = 85.272(10), γ = 75.173(10)°, Z = 2) reveals, that the compound crystallizes as a racemic mixture with C2 point symmetrical complex anions. The bond lengths in both S′‐Pt‐O˙ axes are Pt‐S′ = 2.321 and Pt‐O˙ = 2.048 and in the O‐Pt‐O axis Pt‐O = 2.007Å. The oxalato ligands are nearly plane with O‐C‐C‐O torsion angles of 1.4 — 3.9°. The via S′ bound linear thiocyanate groups are coordinated with Pt‐S′‐C angles of 102.6°. In the vibrational spectra the PtE′ stretching vibrations are observed at 327 — 330 ( 1 ) and 217 — 231 cm—1 ( 2 ). The PtO˙ and PtO stretching vibrations are coupled with internal vibrations of the oxalato ligands and appear in the range of 400 — 800 cm—1. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are fd(PtS′) = 2.08, fd(PtSe′) = 1.78, fd(PtO˙) = 2.45 ( 1 ) and 2.27 ( 2 ) and fd(PtO) = 2.65 ( 1 ) and 2.60 mdyn/Å ( 2 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(195Pt) = 4925.9 ( 1 ), 4783.0 ( 2 ) and δ(77Se) = 161.7 ppm with the coupling constant 1J(SePt) = 366.2 Hz. 相似文献
15.
Synthesis, Crystal Structures, and Vibrational Spectra of [Pt(N3)6]2– and [Pt(N3)Cl5]2–, 195Pt and 15N NMR Spectra of [Pt(N3)nCl6–n]2– and [Pt(15NN2)n(N215N)6–n]2–, n = 0–6 By ligand exchange of [PtCl6]2– with sodium azide mixed complexes of the series [Pt(N3)nCl6–n]2– and with 15N‐labelled sodium azide (Na15NN2) mixtures of the isotopomeres [Pt(15NN2)n(N215N)6–n]2–, n = 0–6 and the pair [Pt(15NN2)Cl5]2–/[Pt(N215N)Cl5]2– are formed. X‐ray structure determinations on single crystals of (Ph4P)2[Pt(N3)6] ( 1 ) (triclinic, space group P1, a = 10.175(1), b = 10.516(1), c = 12.380(2) Å, α = 87.822(9), β = 73.822(9), γ = 67.987(8)°, Z = 1) and (Ph4As)2[Pt(N3)Cl5] · HCON(CH3)2 ( 2 ) (triclinic, space group P1, a = 10.068(2), b = 11.001(2), c = 23.658(5) Å, α = 101.196(14), β = 93.977(15), γ = 101.484(13)°, Z = 2) have been performed. The bond lengths are Pt–N = 2.088 ( 1 ), 2.105 ( 2 ) and Pt–Cl = 2.318 Å ( 2 ). The approximate linear azido ligands with Nα–Nβ–Nγ‐angles = 173.5–174.6° are bonded with Pt–Nα–Nβ‐angles = 116.4–121.0°. In the vibrational spectra the PtCl stretching vibrations of (n‐Bu4N)2[Pt(N3)Cl5] are observed at 318–345, the PtN stretching modes of (n‐Bu4N)2[Pt(N3)6] at 401–428 and of (n‐Bu4N)2[Pt(N3)Cl5] at 408–413 cm–1. The mixtures (n‐Bu4N)2[Pt(15NN2)n(N215N)6–n], n = 0–6 and (n‐Bu4N)2[Pt(15NN2)Cl5]/(n‐Bu4N)2[Pt(N215N)Cl5] exhibit 15N‐isotopic shifts up to 20 cm–1. Based on the molecular parameters of the X‐ray determinations the vibrational spectra are assigned by normal coordinate analysis. The average valence force constants are fd(PtCl) = 1.93, fd(PtNα) = 2.38 and fd(NαNβ, NβNγ) = 12.39 mdyn/Å. In the 195Pt NMR spectrum of [Pt(N3)nCl6–n]2–, n = 0–6 downfield shifts with the increasing number of azido ligands are observed in the range 4766–5067 ppm. The 15N NMR spectrum of (n‐Bu4N)2[Pt(15NN2)n(N215N)6–n], n = 0–6 exhibits by 15N–195Pt coupling a pseudotriplett at –307.5 ppm. Due to the isotopomeres n = 0–5 for terminal 15N six well‐resolved signals with distances of 0.03 ppm are observed in the low field region at –201 to –199 ppm. 相似文献
16.
Crystal Structures, Vibrational Spectra and Normal Coordinate Analysis of fac ‐(Et4N)[OsF3Cl3] and fac ‐(Et4N)[IrF3Cl3] By careful oxidation of the pure fluorochloroosmates(IV) or ‐iridates(IV) with BrF3 or KBrF4 in dichloromethane the mixed pentavalent complex anions fac‐[OsF3Cl3]– and fac‐[IrF3Cl3]– are formed. X‐ray structure determinations on single crystals have been performed of cis‐(Et4N)[OsF3Cl3] ( 1 ) (orthorhombic, space group Pbca, a = 11.225(5), b = 12.020(5), c = 21.873(5) Å, Z = 8) and fac‐(Et4N)[IrF3Cl3] ( 2 ) (orthorhombic, space group Pbca, a = 11.269(10) b = 12.049(1), c = 21.801(3) Å, Z = 8). Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra for the anion of 1 and 2 have been assigned by normal coordinate analysis. The Osmium compound exhibits slightly higher valence force constants as compared with the Iridium complex: fd(OsF) = 3.25, fd(IrF) = 3.25, fd(OsCl) = 2.35 and fd(IrCl) = 2.25 mdyn/Å. 相似文献
17.
Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the mer ‐Trihalogeno‐tris‐Pyridine‐Osmium(III) Complexes mer‐[OsX3Py3], X = Cl, Br, I By reaction of the hexahalogenoosmates(IV) with pyridine and iso‐amylalcohol mer‐trihalogeno‐tris‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of mer‐[OsBr3Py3] (monoclinic, space group P21/n, a = 9.098(5), b = 12.864(5), c = 15.632(5) Å, β = 90.216(5)°, Z = 4) and mer‐[OsI3Py3] (monoclinic, space group P21/n, a = 9.0952(17), b = 13.461(4), c = 15.891(10), β = 91.569(5)°, Z = 4). The pyridine rings are twisted propeller‐like against the N3 meridional plane with mean angles of 49° (Cl), 46° (Br), 44° (I). Based on the molecular parameters of the X‐ray structure determinations and assuming C2 point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis. Due to the stronger trans influence of pyridine as compared with the halide ligands for N'–Os–X · axes significantly different valence force constants are observed in comparison with symmetrically coordinated octahedron axes: fd(OsCl) = 1.74, fd(OsCl·) = 1.49, fd(OsBr) = 1.43, fd(OsBr · ) = 1.18, fd(OsI) = 0.99, fd(OsI · ) = 0.96, fd(OsN) between 1.96 and 2.07 and fd(OsN') between 2.13 and 2.32 mdyn/Å. 相似文献
18.
Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (CH2py2)[Ru(NO)FCl4] By treatment of [Ru(NO)Cl5]2– with a BrF3 saturated frigen solution in dichloromethane the complex [Ru(NO)FCl4]2– is formed, which can be separated from hydrolysis products by ion exchange chromatography on diethylaminoethyl cellulose. The X‐Ray structure determination on a single crystal of (CH2py2)[Ru(NO)FCl4] · 1/2 (CH3)2CO (triclinic, space group P1, a = 9.416(2), b = 14.919(6), c = 15.127(3) Å, α = 61.86(3), β = 80.31(2), γ = 72.49(3)°, Z = 4) reveals, that the fluorine atom is trans positioned to the nitrosyl group. The low temperature IR and Raman spectra have been recorded of (n‐Bu4N)2[Ru(NO)FCl4] and are assigned by normal coordinate analysis. A good agreement between observed and calculated frequencies is achieved. The valence force constants are fd(NO) = 13.92, fd(RuN) = 5.16, fd(RuF) = 3.19 and fd(RuCl) = 1.45 mdyn/Å. The 19F NMR spectra exhibits one singlet at –144.6 ppm. 相似文献
19.
Synthesis, Crystal Structure, and Vibrational Spectra of cis ‐(CH2Py2)[ReBr4Py2]2 · (CH3)2CO By reaction of (n‐Bu4N)2[ReBr6] with pyridine and (n‐Bu4N)BH4 in dichloromethane halogeno‐pyridine‐rhenium(III)complexes are formed and purified by chromatography. X‐ray structure determination on a single crystal has been performed of cis‐(CH2Py2)[ReBr4Py2]2 · (CH3)2CO (monoclinic, space group P21/c, a = 15.0690(9), b = 8.3337(8), c = 35.588(4) Å, β = 96.409(7), Z = 4). Based on the molecular parameters of the X‐ray structure determination and assuming C2 point symmetry for the anion cis‐[ReBr4Py2]– the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are in the Br–Re–Br axis fd(ReBr) = 1.49, in the asymmetrically coordinated N′–Re–Br · axes fd(ReBr · ) = 1.03 und fd(ReN′) = 2.52 mdyn/Å. 相似文献
20.
Syntheses, Vibrational Spectra, and Normal Coordinate Analysis of Halogenonitrosylruthenates [Ru(NO)ClnBr5–n]2–, n = 0–5, and the Crystal Structure of (CH2py2)[Ru(NO)ClBr4] By treatment of [Ru(NO)Cl5]2– with anhydrous HBr in dichloromethane a mixture of [Ru(NO)ClnBr5–n]2–, n = 0–5, is formed, from which individual complexes can be separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determination on a single crystal of (CH2py2)[Ru(NO)ClBr4] (monoclinic, space group P21/c, a = 11.480(2), b = 10.175(4), c = 16.025(6) Å, β = 107.40(1)°, Z = 4) reveals, that the chlorine atom is trans positioned to the nitrosyl group. The low temperature IR and Raman spectra have been recorded of six complexes of the series (n-Bu4N)2[Ru(NO)ClnBr5–n], n = 0–5, and are assigned by normal coordinate analysis. A good agreement between observed and calculated frequencies is achieved. The valence force constants are fd(NO) = 13.86–13.93 und fd(RuN) = 5.43–5.49 mdyn/Å. 相似文献