Tricarbonylrhenium(I) Complexes with N‐Heterocyclic Thiones and Selenols

Anion-Recognition Studies of a Rhenium(I) 4-Mercaptopyridine Compound and Its Ligand-Coupling Products

“…However, this disorder problem seems to cause high deviations for the Re(I)−N distances with values of 2.20(5) and 2.23(3) Å, compared with that of the other compounds, 2.203(5) Å, and indeed these distances are mostly within a normal range. 14 Besides, the S−S distances of 2.012(4) and 2.007(11) Å are normal and comparable to the value of 2.03 Å in the molecular loop of [Pt-(PEt 3 ) 2 (Py 2 S 2 )] 2 (NO 3 ) 4 . 17 Spectroscopic and Emission Properties.…”

“…The Re–S distances of 2.5026(13), 2.5038(14), and 2.5133(13) Å are slightly shorter than the related values of 2.511(2), 2.520(2), and 2.523(1) Å in [Re­(CO) 3 (HSpy) 3 ]­Br, where HSpy and 4-PySH are ortho and para isomers of mercaptopyridines, respectively. Significantly, the C–S distances of 1.714(5) and 1.721(5) Å are comparable to the related values of 1.704(3), 1.708(3), and 1.712(3) Å in [Re­(CO) 3 (HSpy) 3 ]­Br and 1.703(2) Å in free 4-PySH, suggestive of thione rather than thiol character. As a matter of fact, the C–S values were determined by X-ray diffraction to be 1.65–1.71 Å for the normal thione character of the coordinated heterocycles .…”

“…The Re(I) ion, coordinating to three 4-PySH ligands through S atoms and three CO groups in a facial arrangement, adopts a typical octahedral geometry. The Re−S distances of 2.5026(13), 2.5038( 14), and 2.5133(13) Å are slightly shorter than the related values of 2.511(2), 2.520(2), and 2.523(1) Å in [Re(CO) 3 (HSpy) 3 ]Br, 14 where HSpy and 4-PySH are ortho and para isomers of mercaptopyridines, respectively. Significantly, the C−S distances of 1.714 (5) and 1.721 (5) Å are comparable to the related values of 1.704(3), 1.708(3), and 1.712(3) Å in [Re(CO) 3 (HSpy) 3 ]Br 14 and 1.703(2) Å in free 4-PySH, 15 suggestive of thione rather than thiol character.…”

“…This dinuclear Re(I) complex features a molecular loop, where each Re(I) ion with a typical octahedral geometry coordinates to three terminal carbonyl groups, two bridging Py 2 S 2 ligands, and one Cl − anion. The Re(I)−N distance of 2.209(6) Å is mostly within a normal range, 14 whereas the S−S distances of 2.026(6) and 2.049(9) Å are comparable to the value of 2.03 Å in [Pt(PEt 3 ) 2 (Py 2 S 2 )] 2 (NO 3 ) 4 . 17 Moreover, the molecular-loop dimension is 10.78 × 9.34 Å 2 between the Re(I)•••Re(I) ions and midpoints of the S−S bonds, respectively.…”

Rhenium(V) Complexes with Selenolato‐ and Tellurolato‐Substituted Schiff Bases – Released PPh3as a Facile Reductant

“…Only a few of such compounds have been characterized crystallographically . The majority of them contains the metal in low oxidation states and tricarbonylrhenium(I) species dominate . Organoselenolato and ‐tellurolato complexes with rhenium in higher oxidation states are even more scarce despite their proposed potentially beneficial catalytic properties .…”