208041-81-0

Basic information

• Product Name: [CH₃Re(NC₆H₃(CH(CH₃)2)2)(O)2]
• Synonyms: [CH₃Re(NC₆H₃(CH(CH₃)2)2)(O)2]
• CAS NO: 208041-81-0
• Molecular Weight: 408.514
• Mol File: 208041-81-0.mol

Chemical Properties

• CAS DataBase Reference: [CH₃Re(NC₆H₃(CH(CH₃)2)2)(O)2](CAS DataBase Reference)
• NIST Chemistry Reference: [CH₃Re(NC₆H₃(CH(CH₃)2)2)(O)2](208041-81-0)
• EPA Substance Registry System: [CH₃Re(NC₆H₃(CH(CH₃)2)2)(O)2](208041-81-0)

Safety Data

• Hazardous Substances Data: 208041-81-0(Hazardous Substances Data)

Upstream product

• 124943-38-0 tris((2,6-diisopropylphenyl)imido)methylrhenium(VII) 
• 28178-42-9 2,6-diisopropylphenyl isocyanate 
• 70197-13-6 methyltrioxorhenium(VII) 
• 124943-35-7 MeRe(N-2,6-diisopropylphenyl)2O 
• 7732-18-5 water 
• 124943-36-8 MeReO(N(2,6-diisopropylphenyl)2) 

Relevant articles and documents

Preparation, properties, and reactions of five-coordinate Re(VII) dioxo and diimido complexes

The reactions of aliphatic and aromatic 1,2-diamines, diols, and dithiols with CH3ReO3 (1), {CH3Re(NAr)2O}2 (2, Ar = 2,6-diisopropylphenyl), and {CH3Re(NAr)2S}2 (3) have been studied. Two of the reaction products, [CH3Re(O)2{l,2-(NH)2C6H4} ]2{μ-l,2-(NH2)2C6H4} (4a′) and CH3Re(NAr)2(SCH2CH2S) (5c), have been structurally characterized. The former is a binuclear species in which each rhenium is six-coordinate with a pseudo-octahedral structure. The bridging phenylenediamine ligand can be replaced by pyridine and its derivatives. Unlike the known catecholato complex CH3ReVII(O)2(1,2-O2C6H 4)(Py), the Rev-benzoquinonediimine resonance form contributes noticeably to the overall structure of 4a′. The five-coordinate diimido complex 5c does not interact with coordinating ligands such as pyridines. The initial reactions of 2 with catechol and ethylene glycol lead to CH3Re(NAr)2(l,2-O2C6H4) (5b′) and CH3Re(NAr)2(OCH2CH2O) (5b), respectively. Further hydrolysis of 5b affords CH3Re(NAr)-(O)(OCH2CH2O) (6b). Compound 3, a sulfur analogue of 2, condenses only with dithiols. The high reactivity of 2 is likely due to the presence of a four-coordinate monomeric form in solution and the formation of H2O with strong O - H bonds as a byproduct.

Hydrolysis, hydrosulfidolysis, and aminolysis of imido(methyl)rhenium complexes

The tris(imido)methylrhenium complex CH3Re(NAd)3 (1a, Ad = 1-adamantyl) reacts with H2O to give CH3Re(NAd)2O (2a) and AdNH2. The resulting di(imido)oxo species can further react with another molecule of H2O to generate CH3Re(NAd)O2 (3a). The kinetics of these reactions have been studied by means of 1H NMR and UV-vis spectroscopies. The second-order rate constant for the reaction of 1a with H2O at 298 K in C6H6 is 3.3 L mol-1 s-1, which is much larger than the value 1 x 10-4 L mol-1 s-1 obtained for the reaction between CH3Re(NAr)3 (1b, Ar = 2,6-diisopropylphenyl) and H2O in CH3CN at 313 K. Both 1a and 1b react with H2S to produce the rhenium(VII) sulfide, {CH3Re(NR)2}2(μ-S)2 (4a, R = Ad; 4b, R = Ar), with second-order rate constants of 17 and 1.6 x 10-4 L mol-1 s-1 in C6H6 and CH3CN, respectively. Complex 4b has been structurally characterized. The crystal data are as follows: space group C2/c, a = 30.4831 (19) A, b = 10.9766 (7) A, c = 18.1645 (11) A, β = 108.268(1)°, V = 5771.5 (6) β3, Z = 4. The reaction between CH3Re(NAr)2O (2b) and H2S also yields the dinuclear compound 4b. Unlike 1b, 1a reacts with aniline derivatives to give mixed imido rhenium complexes.

Organorhenium imido complexes: Syntheses, structure, and reactivity

Imido complexes of heptavalent rhenium have been synthesized by three different routes: (i) aminolysis of the half-sandwich complex (η5-C5Me5)ReCl4 (1) (Me = CH3) with primary amines gives the imido derivatives (η5-C5Me5)Re(NtBu)Cl2 (2a, tBu = tert-butyl) and (η5-C5Me5)Re(NCH3)Cl2 (2b). The rhenium-nitrogen distance in compound 2a (1.709 (3) A?) corresponds to a triple bond (single-crystal X-ray diffraction), while the analogous oxo congener (η5-C5Me5)ReOCl2 has relatively little rhenium-oxygen triple-bond character, (ii) Sequential deoxygenation of methyltrioxorhenium(VII) (6) via decarboxylation upon treatment with 2,6-diisopropylphenyl isocyanate yields mono- and dinuclear methylrhenium(VII) imido complexes 7-9 in good yields; imido bridging occurs when the mononuclear compounds of types CH3ReO(NR)2 (8a) and CH3Re(NR)3 (9a) are dissolved in polar solvents such as typically 1,2-dimethoxyethane. (iii) Nucleophilic substitution of Me3SiO-Re(NtBu)3 (10) by organolithium or Grignard reagents was used to synthesize the new methyl-, allyl-, ethyl-, and phenylalkynyl derivatives R′-Re(NtBu)3 (R′ = CH3, 11a; C3H5, 11b; C2H5, 11c; C6H5C≡C, 11d). These compounds are thermally very robust even though 11b,c exhibit alkyl groups with β-hydrogen atoms. σ- instead of π-coordination of the allyl ligand of 11b underlies the strong electron-releasing character of the three imido ligands; this suggests that even π-ligands R′ in compounds of type R′-Re(NR)3 will be only σ-coordinated, in contrast to the oxo congeners R′-ReO3. [2 + 2] Cycloaddition intermediates can be trapped in the reaction of the oxorhenium(III) alkyne complexes of type (η5-C5Me5)ReO(η 2-RC≡CR) (3a, R = CH3; 3b, C6H5) with phenyl isocyanate to give phenyl carbamidato-N,O complexes 4a,b that undergo consecutive decarboxylations and isocyanate addition to yield finally ureato-N,N′ compounds 5a,b.