94405-83-1

Upstream product

• 92786-90-8 {Cp*Re(CO)2(p-N₂C₆H₄OMe)}{BF₄} 
• 94405-84-2 (C₅(CH₃)5)Re(CO)(COO)(N₂C₆H₄OCH₃)^(1-)*Li⁽¹⁺⁾ = [(C₅(CH₃)5)Re(CO)(COO)(N₂C₆H₄OCH₃)]Li 
• 16940-66-2 sodium tetrahydroborate 
• 101835-38-5 {Cp*Re(CO)(PMe₃)(p-N₂C₆H₄OMe)}{BF₄} 
• 117119-80-9 {Cp*Re(CO)(PPh₃)(p-N₂C₆H₄OMe)}{BF₄} 

Relevant academic research and scientific papers

Rhenium carbonyl phosphine dinitrogen complexes (η5-C5Me5)Re(CO)(PR3)(N 2)

The new rhenium dinitrogen complexes (η5-C5Me5)Re(CO)(PR3)(N 2) (3a-f) have been synthesized for PR3 = (a) PMe3, (b) P(n-Bu)3, (c) PCy3 (Cy = cyclohexyl), (d) PPh3, (e) P(OMe)3, and (f) P(OCH2)3CMe by treatment of the corresponding p-methoxyphenyldiazenido complexes [(η5-C5Me5)Re(CO)(PR3)(p-N 2C6H4OMe)][BF4] (2a-f) with t-BuLi. These cationic phosphine complexes 2a-f were synthesized from the cationic acetonitrile complex [(η5-C5Me5)Re(CO)(NCMe)(p-N 2C6H4OMe)][BF4] (1a) and the appropriate phosphine. The compounds have been characterized spectroscopically, including unambiguous 15N and 14N NMR assignments of the Nα and Nβ resonances of the aryldiazenide and dinitrogen ligands. Comparisons are made with the properties of the related known dicarbonyl compounds [(η5-C5Me5)Re(CO)2(p-N 2C6H4OMe)][BF4] and (η5-C5Me5)Re(CO)2(N 2). It is shown that the 15N label in 15Nα-labeled 2a and 2e is retained exclusively at the Nα position in the dinitrogen complexes 3a and 3e; however, an equimolar mixture of 15Nα- and 15Nβ-labeled (η5-C5Me5)Re(CO)2( 15N14N) results when this dinitrogen complex is synthesized from exclusively 15Nα-labeled [(η5-C5Me5)Re(CO)2(p- 15N14NC6H4OMe)][BF4]. Hexane or cyclohexane solution IR spectra of 3d (PR3 = PPh3) and 3e (PR3 = P(OMe)3), but not of the remainder, show two ν(NN) absorption bands. This is attributed to the existence of more than one possible conformation of the PR3 ligand in these complexes. The N2 ligand in 3a (PR3 = PMe3) is remarkably inert, as it is not displaced by PPh3 at room temperature in diethyl ether solution and shows no exchange with nitrogen gas when pressurized.

Syntheses, X-ray structures, and cis-trans isomerism of (pentamethylcyclopentadienyl)dicarbonylrhenium dihalides, (η-C5Me5)Re(CO)2X2 (X = Cl, Br, I)

Cis and trans isomers have been synthesized for the series of rhenium dicarbonyl dihalides Cp*Re(CO)2X2 (Cp* = η-C5Me5; X = Cl, Br, I). The cis isomers were formed by reaction of Cp*Re(CO)2(N2) with HX and were converted to the trans isomers by UV irradiation in hexane. The structures of the isomers have been assigned from examination of v(CO) IR intensities and are supported by X-ray structure determinations on cis-Cp*Re(CO)2I2 and trans-Cp*Re(CO)2Br2. Crystal data for cis-Cp*Re(CO)2I2: monoclinic P21/n, a = 7.201 (3) A?, b = 27.254 (5) A?, c = 8.682 (2) A?, β = 110.04 (4)°, U = 1600.2 (2) A?3, Dcalcd = 2.62 g cm-3, Dmeasd = 2.64 (1) g cm-3, Z = 4, λ(Mo Kα) = 0.71069 A?, μ(Mo Kα) = 115.1 cm-1, RF = 0.046, RwF = 0.058 for 1510 observed reflections (2081 measured with 3° ≤ 2θ ≤ 45°). Crystal data for trans-Cp*Re(CO)2Br2: monoclinic P21/c, a = 8.512 (2) A?, b = 12.610 (4) A?, c = 13.794 (6) A?, β = 102.40 (3)°, U = 1446.1 (3) A?3, Dcalcd = 2.47 g cm-3, Dmeasd = 2.43 (1) g cm-3, Z = 4, λ(Mo Kα) = 0.71069 A?, μ(Mo Kα), = 139.8 cm-1, RF = 0.043, RwF = 0.054 for 1509 reflections (2008 measured with 3 ≤ 2θ ≤ 46°). cis- and trans-CpRe(CO)2Cl2 (the missing members of the cyclopentadienyl analogues CpRe(CO)2X2) have been synthesized from CpRe(CO)2(N2) and Cl2. The reaction of Cp*Re(CO)3 with I2 in hexane yields [Cp*Re(CO)3I][I3] thermally and trans-Cp*Re(CO)2I2 after irradiation.

Aryldiazenido (N2Ar) complexes. Carboxylate, formate, hydroxycarbonyl, and hydride derivatives of [(η-C5H5)Re(CO)2(N2Ar)][BF 4] and [(η-C5Me5)Re(CO)2(N2Ar)][BF 4]

The aryldiazenido complexes [(η-C5H5)Re(CO)2(p-N2C 6H4R)][BF4] (1: a, R = Me; b, R = OMe; c, R = NEt2) and [(η-C5Me5)Re(CO)2(p-N2C 6H4R)][BF4] (7, R = OMe) react with a stoichiometric amount of 0.1 M aqueous NaOH to give the air-stable, microcrystalline, golden yellow hydroxycarbonyl complexes (η-C5H5)Re(CO)(p-N2C6H 4R)(COOH) (2) and (η-C5Me5)Re(CO)(p-N2C6H 4R)(COOH) (8). These complexes dissolve in excess aqueous hydroxide to give bright yellow solutions of the respective carboxylate complex anions [(η-C5H5)Re(CO)(p-N2C6H 4R)(CO2)]- (4) and [(η-C5Me5)Re(CC)(p-N2C6H 4R)(CO2)]- (10), which have been isolated as lithium or calcium salts. Under specified conditions, which are discussed, decarboxylation occurs to yield the yellow hydride complexes (η-C5H5)ReH(CO)(p-N2C6H 4R) (3) and (η-C5Me5)ReH(CO)(p-N2C6H 4R) (9). Formate complexes (η-C5H5)Re(CO)(p-N2C6H 4R)(OCHO) (5) and (η-C5Me5)Re(CO)(p-N2C6H 4R)(OCHO) (11), isomeric with the hydroxycarbonyl complexes, have also been synthesized for comparison.