Synthesis and structure of dilithium octamethyldirhenate(III)

Cotton, F. Albert; Gage, Larry D.; Mertis, Kostas; Shive, Larry W.; Wilkinson, Geoffrey

doi:10.1021/ja00438a029

Cited by 39 publications

(16 citation statements)

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“…459 Thus, octamethyldirhenium shows eclipsed methyl groups (75) quadruple bond joining the metals in these complexes. 447 The structures of some other dimeric species are shown in Scheme 27 along with the paths by which these derivatives have been formed. Structures of a trimeric alkyl complex and its bis(ligand) adduct are shown as (76) and (77).…”

Section: 622 Alkyi and Aryl Derivatives Of Rhenium Unaccompaniedmentioning

confidence: 99%

Technetium and Rhenium

Boag

Kaesz

1982

Comprehensive Organometallic Chemistry

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Section: 622 Alkyi and Aryl Derivatives Of Rhenium Unaccompaniedmentioning

confidence: 99%

Technetium and Rhenium

Boag

Kaesz

1982

Comprehensive Organometallic Chemistry

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“…Technetium(II)–alkynyl compounds should be obtained from the reaction of Tc 2 Cl 4 (PMe 3 ) 4 with LiCCR (R = Me, Pr, Bu, SiMe 3 , Ph) in dimethoxyethane 36. The [{Li(Et 2 O) 2 }] 2 Tc 2 Me 8 salt should be obtained from the reaction of Tc 2 (O 2 CCH 3 ) 4 Cl 2 with MeLi in diethyl ether,37 while Tc 2 (C 3 H 5 ) 4 should be possible to obtain from the reaction of TcX 4 (X = Cl, Br) with Mg(C 3 H 5 )Cl in diethyl ether 38. Current synthetic efforts on technetium organometallic compounds are in progress, and the results will be reported in due course.…”

Section: Discussionmentioning

confidence: 99%

A Decade of Dinuclear Technetium Complexes with Multiple Metal–Metal Bonds

et al. 2014

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Transition metal complexes with multiple metal–metal bonds exhibit interesting catalytic and biological properties. One element whose metal–metal bond chemistry has been poorly studied is technetium. Currently, only 25 technetium complexes with multiple metal–metal bonds have been structurally characterized. The nature of metal–metal interactions in these complexes, as well as the influence of ligands on the bonding in the Tc2n+ unit (n = 6, 5, 4) are not well understood. In order to better understand the influence of ligands on the Tc–Tc bonding, a study of the solid‐state and electronic structure of dinuclear complexes with the Tc2n+ unit (n = 6, 5, 4) has been performed. Dinuclear technetium complexes (nBu4N)2Tc2X8, Tc2(O2CCH3)4X2, Tc2(O2CCH3)2Cl4, cesium salts of Tc2X83–, and Tc2X4(PMe3)4 (X = Cl, Br) were synthesized; their molecular and electronic structures, as well as their electronic absorption spectra, were studied by a number of physical and computational techniques. The structure and bonding in these systems have been investigated by using multiconfigurational quantum calculations. For all these complexes, the calculated geometries are in very good agreement with those determined experimentally. Bond order analysis demonstrates that all these complexes exhibit a total bond order of approximately 3. Analysis of individual effective bond order (EBO) components shows that these complexes have similar σ components, while the strength of their π components follows the order Tc2X4(PMe3)4 > Tc2X83– > Tc2(O2CCH3)2Cl4 > Tc2X82–. Calculations indicate that the δ components are the weakest bond in Tc2X8n– (n = 2, 3) and Tc2(O2CCH3)2Cl4. Further analysis of Tc2X83– and Tc2X4(PMe3)4 (X = Cl, Br) indicates that the electronic structure of the Tc25+ and Tc24+ units is insensitive to the nature of the coordinating ligands. The electronic absorption spectra of Tc2X8n– (n = 2, 3), Tc2(O2CCH3)2Cl4, and Tc2X4(PMe3)4 (X = Cl, Br) were studied in solution, and assignment of the transitions was performed by multiconfigurational quantum chemical calculations. For the Tc2X8n– (n = 2, 3; X = Cl, Br) anions and Tc2(O2CCH3)2Cl4, the lowest‐energy band is attributed to the δ→δ* transition. For Tc2X4(PMe3)4, the assignment of the transitions follow the following order in energy: δ*→σ* < δ*→π* < δ→σ* < δ→π*.

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“…There are Mo-Mo bonds in these clusters, but not multiple ones (17). Polarized crystal spectra (19) for K^Mo2(SO^)^ « 2H2O, 4which the Mo2(S0^)^ ion has four bridging sulfates, have indicated a band at 19,400 cm ^ with a polarization consistent with a 6 6* assignment. Also, for K^Mo2(S0^) 3.5 H2O, in which one electron from the quadruple bond has been lost by oxidation, the first band with an origin at about 6,300 cm~^ has the polarization predicted for the 5 • S* assignment (20).…”

Section: Cre2clgjmentioning

confidence: 65%

“…Re quadruple bond lengths is from 2.178 (1) in Re2Meg ion (6) to about 2.24 A in several compounds (7), e.g., Re2Clg~ salts.…”

Section: -mentioning

confidence: 99%

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Single-crystal polarized electronic spectra of the compounds dichlorotetrakis ([mu]-pivalato)dirhenium(III),tetra-n-butylammonium octachlorodirhenate(III), tetra-n-butylammonium octabromodirhenate(III), dimolybdenum(II)tetrapivalate, and the X-ray diffraction cyrstal structures of tetra-n-butylammonium octobromodirhenate(III) and two polymorphs of dimolybdenum(II) tetrapivalate

Huang¹

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Recommended Citation Huang, Hai-Wei, "Single-crystal polarized electronic spectra of the compounds dichlorotetrakis ([mu]-pivalato)dirhenium(III),tetran-butylammonium octachlorodirhenate(III), tetra-n-butylammonium octabromodirhenate(III), dimolybdenum(II)tetrapivalate, and the X-ray diffraction cyrstal structures of tetra-n-butylammonium octobromodirhenate(III) and two polymorphs of dimolybdenum(II) tetrapivalate " (1985). Retrospective Theses and Dissertations. 8704. https://lib.dr.iastate.edu/rtd/8704 EXPERIMENTAL 24 Preparation 24 Crystal Optics and Spectra 26 Polarization Ratios 37 Crystallographic Indexing 41 X-ray Data Collection and Structure Solution 42 General 42 [N(n-C^Hg)^]2Re2Brg 43 CN(n-C^Hg)^l2^e2Clg 45 Re2[02CC(CHg)^]^Cl2 46 The monoclinic crystals of E-MO^CO^CCCCHG)^)^ 46 The orthorhomhic crystals of Y-Mo2(02CC(CHg)g)^ 47 RESULTS AND DISCUSSION 50 Description of Crystal Structures 50 Structure of CN(n-C^Hg)^32^e2Brg 50 Structures of M02 (^2^^^ ""^3 ^3^4 57 Crystal Spectra 73 CN(n-C^Hg)^32Re2Clg 73 CN(n-C^Hg)^32^®2®^8 83 iii Comparison of (TEA)2Re2Clg and (TBA)2Re2Brg 96 Re2i:02CC(CH3)3D^Cl2 98 The monoclinic Mo2(02CC(CH3)g)^ 107 The orthorhombic MO2(^2^^^ ^^3 ^3^4 120

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Synthesis and structure of dilithium octamethyldirhenate(III)

Cited by 39 publications

References 2 publications

Technetium and Rhenium

Technetium and Rhenium

A Decade of Dinuclear Technetium Complexes with Multiple Metal–Metal Bonds

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