Einkristall‐ Röntgenstrukturanalysen an Verbindungen mit kovalenter Metall‐Metall‐Bindung.VI. Die kristall‐und Molekülstruktur von Bromozinn(IV)‐tris(pentacarbonylmangan) und Octacarbonylbis[μ‐chlorozinn(IV)‐(pentacarbonylmangan)]di mangan (Mn ‐ Mn)

Haupt, H.‐J.; Preut, H.; Wolfes, W.

doi:10.1002/zaac.19784460111

Zeitschrift anorg allge chemie

1978

DOI: 10.1002/zaac.19784460111

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Einkristall‐ Röntgenstrukturanalysen an Verbindungen mit kovalenter Metall‐Metall‐Bindung.VI. Die kristall‐und Molekülstruktur von Bromozinn(IV)‐tris(pentacarbonylmangan) und Octacarbonylbis[μ‐chlorozinn(IV)‐(pentacarbonylmangan)]di mangan (Mn ‐ Mn)

H.‐J. Haupt¹,

H. Preut²,

W. Wolfes³

Abstract: BrSn[Mn(Co)5]3 besitzt am Sn(IV)‐Atom ein verzerrtes Tetraeder: MnSnMn‐Winkel (Mittel) = 116,41(5)° und BrSnMn (Mittel) = 101,05(4)°. Die unterschiedlichen SnMn‐Bindungsabstände (273,9(2) pm; 272,2(2) pm; 275,8(2) pm); resultieren wahrscheinlich aus der intramolekularen Wechselwirkung der sperrigen Mn(CO)5‐Liganden. Das zentrale Molekülfragment von Mn2(CO)8[μ‐Sn(CI)Mn(CO)5]2 besteht aus einem planaren Mn2Sn2‐Rhombus, der quer durch den Ring eine MnMnBindung von 309, 1(1) pm enthält. Neben den beiden Mn‐… Show more

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Cited by 16 publications

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“…Complex 2 reveals some remarkable structural features. The Mn–Sn bond of 2 [2.3997(3) Å] is shorter than all previously reported Mn–Sn double bonds (2.44–2.52 Å) and is also considerably shorter than Mn–Sn single bonds (median value 2.625 Å) . This suggests a strong Mn–Sn bonding interaction in 2 .…”

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confidence: 69%

Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)₂Mn≡Sn(C₆H₃-2,6-Mes₂)]⁺ (dmpe = Me₂PCH₂CH₂PMe₂, Mes = 2,4,6-Trimethylphenyl)

et al. 2013

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A new approach to the first complex featuring a manganese-tin triple bond that takes advantage of the propensity of dihydrogen complexes to eliminate H2 is reported. Reaction of the 18-valence-electron manganese dihydrogen hydride complex [MnH(η(2)-H2)(dmpe)2] (1) (dmpe = Me2PCH2CH2PMe2) with the organotin(II) chloride SnCl(C6H3-2,6-Mes2) (Mes = 2,4,6-trimethylphenyl) selectively afforded by H2 elimination the chlorostannylidene complex trans-[H(dmpe)2Mn═Sn(Cl)(C6H3-2,6-Mes2)] (2), which upon treatment with Na[B(C6H3-3,5-(CF3)2)4] and Li[Al(OC(CF3)3)4] was transformed quantitatively into the stannylidyne complex salts trans-[H(dmpe)2Mn≡Sn(C6H3-2,6-Mes2)]A [A = B(C6H3-3,5-(CF3)2)4 (3a), Al(OC(CF3)3)4 (3b)]. Complexes 2 and 3a/3b were fully characterized, and the structures of 2 and 3a were determined by single-crystal X-ray diffraction. Complex 2 features the shortest Mn-Sn double bond reported to date, a large Mn-Sn-Caryl bond angle, and a long Sn-Cl bond of the trigonal-planar-coordinated tin center. These bonding features can be rationalized in valence-bond terms by a strong contribution of the triply bonded resonance structure [LnMn≡SnR]Cl and were verified by a natural resonance theory (NRT) analysis of the electron density of the DFT-minimized structure of 2. Complex 3a features the shortest Mn-Sn bond reported to date and a linearly coordinated tin atom. Natural bond order and NRT analyses of the electronic structure of the complex cation in 3a/3b suggested a highly polar Mn-Sn triple bond with a 65% ionic contribution to the NRT Mn-Sn bond order of 2.25. Complex 3a undergoes reversible one-electron reduction, suggesting that open-shell stannylidyne complexes might be accessible using strong reducing agents.

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Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)₂Mn≡Sn(C₆H₃-2,6-Mes₂)]⁺ (dmpe = Me₂PCH₂CH₂PMe₂, Mes = 2,4,6-Trimethylphenyl)

et al. 2013

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μ‐Allenyliden‐dimangan‐ und ‐dirhenium‐Komplexe

et al. 1984

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Die Synthesen einer Nonacarbonyl-CI-(di-tert-butylallenyliden)-dimangan-Verbindung (la) und eines isomeren Rheniumkomplexes 1 b mit terminal gebundenem Allenyliden-Rest werden beschrieben. Die Hauptprodukte bei diesen Umsetzungen zu l a bzw. l b stellen die (3-terf-Butyl-3-hydroxy-4,4-dimethyl-l-pentinyl)pentacarbonylmangan-bzw. -rhenium-Verbindungen 2a bzw. 2b dar, die auch auf einem unabhangigen Wege erhalten werden konnen. l a wurde durch eine Rontgenstrukturanalyse charakterisiert. p-Allenylidene-dimanganese and -dirhenium ComplexesThe syntheses of a nonacarbonyl-~-(di-ferf-butylallenylidene)-dimanganese compound (1 a) and of an isomeric rhenium complex 1 b containing a terminal allenylidene residue are described. A (3-ferr-butyl-3-hydroxy-4,4-dimethyl-l-pentynyl)pentacarbonylmanganese (2a) and the corresponding rhenium complex (2b) are the main products in these reactions. 2a and 2b can also be obtained in an independent way. The structure of l a has been determined by an X-ray analysis.In den letzten Jahren konnte eine Reihe von stabilen Komplexen'-6' mit dem ungesattigten Allenyliden-Rest, IC = C = CR2, dargestellt werden. Der cumulierte Carbenligand wurde in einigen Verbindungsbeispielen 3.4) in briickenstandiger Stellung angetroffen.Wir wandten uns der Synthese von p-Allenyliden-dimangan-und -dirhenium-Komplexen zu, um insbesondere den Aspekt der Verbruckungstendenz von Allenyliden-Liganden eingehender betrachten zu konnen.Unter den Synthesewegen zu Diorganylallenyliden-Verbindungen erwiesen sich Eliminierungsprozesse, wie die Desoxygenierung von metallgebundenen tert-PropargylatEinheiten als vorteilhaft2-5' [GI. (I)].2 H+ ode: COCI,Fur eine Nutzung dieser Schliisselreaktion im Bereich der Substitutionsderivate von M2(CO)lo-Verbindungen (M = Mn, Re) wurde zunachst die Fixierung des Di-tertbutylpropargylat-Ions an M,(CO)s-Einheiten (M = Mn, Re) studiert. Resultate und Diskussion

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Octacarbonylbis {μ‐(tris(trimethylsilyl)methyl]indany l} dimanganese with Two Monoalkyl Indium Groups Bridging the Mn–Mn Bond

et al. 1995

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Key Words: Tetraindane(4) / Indium@) I Mn-Mn bond / Indium alkyl bridge Tetrclhedra-tetrakis[tris(trimethylsilyl)methyl]tetraindane(4)(1) reacts with decacarbonyldimanganese(0) to yield the bright red crystalline title compound 2, in which two and a planar MnzInz molecular center. carbonyl ligands are replaced by two InR fragments. The crystal structure determination of 2 shows two M n ( C 0 ) 4 groups (Mn-Mn 313.7 pm) bridged by two monoalkylindium units Recently, we succeeded in synthesizing and determining the crystal structure of the alkylindium(1) compound I I I~[ C ( S~M~~)~]~ (1) with a nearly undistorted tetrahedral In4 skeleton in the solid state"], which in contrast to the Ga4 analog[*] remains tetrameric in dilute benzene solutions. In the course of systematic investigations of the chemical properties of 1[1,3] we found that the monomeric In-C(SiMe& fragment is able to substitute carbonyl ligands in transition metal carbonyls. In this paper we report on the reaction of 1 with Mn2(CO)lo. Reaction of In4[C(SiMe3)3]4 with Mnz(CO)loMixtures of 1 and Mnz(CO)lo in n-hexane remain unchanged at room temperature for several days, while in boiling hexane the characteristically deep violet color of 1 disappears within two or three hours, depending on the excess of the manganese carbonyl used. A dark red solution is formed, from which after concentration and recrystallization dark red, very fine needles of the title compound 2 are isolated in 60% yield. The molar mass, cryoscopically determined in benzene solution, and the mass spectrum with a very characteristic isotopic pattern show that two carbonyl groups of the Mn2(CO)lo molecule are replaced by two monoalkylindium fragments [eq. The trimethylsilyl groups of 2 show one resonance in both the 'H-and I3C-NMR spectra. Although the molecular structure of 2 exhibits two chemically different carbonyl groups, only one I3C resonance is observed even at -65°C with the chemical shift 8 = 218. The assignment of the a-carbon atom of the tris(trimethy1si-1yl)methyl group in the 13C-NMR spectrum is not beyond doubt: there is only one further signal at 6 = 51.7 lying more than 25 ppm downfield with respect to the region normally observed for carbon atoms bound to indiumL61. The location of this carbon atom in the nodal plane of the p orbital, which is perpendicular to the molecular plane and can accept x electron density by backdonation, might be responsible for this unusual shift. Figure 1 shows the molecular structure of 2. Molecule 2 contains an Mn -Mn bond bridged by two monoalkylindium fragments. Crystal Structure of 2Whereas several compounds with bridged Mn-Mn bonds are known ['], only a few examples exhibit a bridging third main group element[8-'01. Indium as a bridging atom is mostly tetracoordinatedL9I, a lower coordination number is found in a dimanganese compound bridged by an In-Mn(CO)5 group[l0I. To our knowledge bridging alkylindium units with tricoordinated In atoms like in 2 have previously not been described. The synthesis according to eq. (1) therefore ope...

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Einkristall‐ Röntgenstrukturanalysen an Verbindungen mit kovalenter Metall‐Metall‐Bindung.VI. Die kristall‐und Molekülstruktur von Bromozinn(IV)‐tris(pentacarbonylmangan) und Octacarbonylbis[μ‐chlorozinn(IV)‐(pentacarbonylmangan)]di mangan (Mn ‐ Mn)

Cited by 16 publications

References 18 publications

Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)₂Mn≡Sn(C₆H₃-2,6-Mes₂)]⁺ (dmpe = Me₂PCH₂CH₂PMe₂, Mes = 2,4,6-Trimethylphenyl)

Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)₂Mn≡Sn(C₆H₃-2,6-Mes₂)]⁺ (dmpe = Me₂PCH₂CH₂PMe₂, Mes = 2,4,6-Trimethylphenyl)

μ‐Allenyliden‐dimangan‐ und ‐dirhenium‐Komplexe

Octacarbonylbis {μ‐(tris(trimethylsilyl)methyl]indany l} dimanganese with Two Monoalkyl Indium Groups Bridging the Mn–Mn Bond

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Einkristall‐ Röntgenstrukturanalysen an Verbindungen mit kovalenter Metall‐Metall‐Bindung.VI. Die kristall‐und Molekülstruktur von Bromozinn(IV)‐tris(pentacarbonylmangan) und Octacarbonylbis[μ‐chlorozinn(IV)‐(pentacarbonylmangan)]di mangan (Mn ‐ Mn)

Cited by 16 publications

References 18 publications

Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)2Mn≡Sn(C6H3-2,6-Mes2)]+ (dmpe = Me2PCH2CH2PMe2, Mes = 2,4,6-Trimethylphenyl)

Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)2Mn≡Sn(C6H3-2,6-Mes2)]+ (dmpe = Me2PCH2CH2PMe2, Mes = 2,4,6-Trimethylphenyl)

μ‐Allenyliden‐dimangan‐ und ‐dirhenium‐Komplexe

Octacarbonylbis {μ‐(tris(trimethylsilyl)methyl]indany l} dimanganese with Two Monoalkyl Indium Groups Bridging the Mn–Mn Bond

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Product

Resources

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Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)₂Mn≡Sn(C₆H₃-2,6-Mes₂)]⁺ (dmpe = Me₂PCH₂CH₂PMe₂, Mes = 2,4,6-Trimethylphenyl)

Manganese–Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)₂Mn≡Sn(C₆H₃-2,6-Mes₂)]⁺ (dmpe = Me₂PCH₂CH₂PMe₂, Mes = 2,4,6-Trimethylphenyl)