Organometallic Compounds of the Lanthanides. 168 [1] Lanthanidocene Complexes containing Sulfur‐functionalized Cyclopentadienyl Ligands

Abstract

YCl3, SmCl3, and LuCl3 react with 2 equivalents of Na[C5H4CH2CH2SR] (R = Ph (2); Et (3)) yielding (PhSCH2CH2C5H4)2LnCl (Ln = Y (4a), Sm (4b), Lu (4c)), and (EtSCH2CH2C5H4)2LuCl (5), respectively. Methylation of 4a, 4c, and 5 with LiMe produces (PhSCH2CH2C5H4)2LnMe (Ln = Y (6a); Lu (6c)) and (EtSCH2CH2C5H4)2LuMe (7). YCl3 and LuCl3 react with 1 equivalent of 2 or 3 followed by 1 equivalent Na[C5Me5] to give (PhSCH2CH2C5H4)(C5Me5)LnCl (Ln = Y (8a); Lu (8c)) and (EtSCH2CH2C5H4)(C5Me5)YCl (9). [(EtSCH2CH2C5H4)(C5Me5)LuCl (10) and 1, 10‐bipyridine form [(EtSCH2CH2C5H4)(C5Me5)Lu(bipy)]+ [(EtSCH2CH2C5H4)(C5Me5)LuCl2]— (11). Methylation of 8a, 8c, and 9 with LiMe results in the formation of (PhSCH2CH2C5H4)(C5Me5)LnMe (Ln = Y (12a); Lu (12c)) and (EtSCH2CH2C5H4)(C5Me5)YMe (13). LaCl3 and PrCl3 react with 3 equivalents of 3 affording (EtSCH2CH2C5H4)3Ln (Ln = La (14d) and Pr (14e)), while the reaction of YbI2 with 2 equivalents of 3 gives [(EtSCH2CH2C5H4)Yb(SCH2CH2C5H4)]2 (15) along with ethane. The structures of 8c, 11, 14d, and 15 were determined by single‐crystal X‐ray diffraction.

A Structural Investigation of Trivalent and Divalent Rare Earth Thiocyanate Complexes Synthesised by Redox Transmetallation

“…All RE–S bond lengths are very long. Thus, La–S of eight‐coordinate 3b [3.121(2) Å] approaches La–S(thioether) [3.191(2), 3.237(2) Å] of eleven ‐coordinate [La(η 5 ‐C 5 H 4 CH 2 CH 2 SEt) 3 ],39a whilst Y–S of ( 3a ) [3.1051(7) Å] is much longer than Y–S(thioether) [2.9572(6), 2.9379(6) Å] of nine‐coordinate [Y(η 5 ‐C 5 H 4 CH 2 CH 2 SEt) 2 Cl],39b indicating the S donor atoms of 3a , b are behaving as neutral donors (S = C=N – ). By contrast, C 6 F 5 S – in [Er(SC 6 F 5 ) 3 (dme) 2 ] has Er–S [2.694(2)–2.722(1) Å],39c much shorter than in 3g .…”

Stabilization of propene molybdenum and tungsten half–sandwich complexes by intramolecular coordination of a thioether function

“…The substituted cyclopentadiene was prepare using modification of the previously described procedures. 46,47…”

“…The substituted cyclopentadiene was prepare using modication of the previously described procedures. 46,47 Freshly monomerized cyclopentadiene (5.2 mL, 62 mmol) was added dropwise to a suspension of sodium sand (1.6 g, 70 mmol) in 30 mL of THF. The mixture was stirred at room temperature for 16 h and then it was ltered from excess of sodium using a Schlenk frit.…”

18 Scandium, yttrium, the lanthanides and the actinides

“…, and [(EtSCH 2 CH 2 C 5 H 4 ) 3 Ln] (Ln = La, Pr) have also been reported. 135 Unusual fluorenyls [(Cp-CMe 2 -Flu) 2 Ln] 2 [Li(ether) n ] 1 (Ln = Y, La) have been made. 136 The first heteroleptic bisphosphanylamide complex of the lanthanides, [(g 5 -Cp*) 2 Sm{g 2 -N(PPh 2 ) 2 }] has been synthesised by routes including a one pot synthesis from SmCl 3 and [K(THF) n ][N(PPh 2 ) 2 ] and KCp*.…”