Trapping CS₂^2– and S₃^2– between Two Ytterbium Formamidinates

Abstract

Treatment of [Yb II (DippForm) 2 (thf) n ] (n = 2 (1aYb), n = 1 (1bYb); DippForm = N,N′-bis(2,6-diisopropylphenyl)f o r m a m i d i n a t e ), w i t h e i t h e r e x c e s s C S 2 o r S 8 g i v e s [Yb III 2 (DippForm) 4 (CS 2 )] (3) and [Yb III 2 (DippForm) 4 (S 2 ) 0.5 /(S 3 ) 0.5 ] (4) respectively. 3 is a new addition to an exclusive class of compounds containing the CS 2 2− dianion, and 4 is the first crystallographically characterized example of a rare-earth trisulfide complex.

3d–4f heterometallic complexes by the reduction of transition metal carbonyls with bulky LnII amidinates

“…By using different electronic and steric environments around divalent lanthanide elements, a different reactivity can be achieved with a same substrate. [37][38][39][40][41][42][43][44][45] 42 In addition, activation of white phosphorous and yellow arsenic by [(DippForm) 2 Sm II (thf ) 2 ] led to the formation of [{(DippForm) 2 Sm III } 2 (μ-η 4 -Pn 4 )] (Pn = P, As). 43 These products contrast with the cage-type molecules [{Cp* 2 Sm III } 4 (Pn) 8 ] (Pn = P, 37 As, 44 and Sb 47 ) that were obtained by reaction of [Cp* 2 Sm II ] with white phosphorous, nanoscale arsenic, and nanoscale antimony, respectively.…”

CS2 Reductive Coupling to Acetylenedithiolate by a Dinuclear Ytterbium(II) Complex

“…Previous studies have shown that the reactiono fL n II with sulfur can yield dinuclear sulfide, disulfide, trisulfide and polysulfide complexes or fascinating sulfide-bridged cluster compounds. [9,19] The reduction of CS 2 to acetylenedithiolate is unprecedented both in f-and d-block metal chemistry.T herefore, DFT calculations (B3PW91) werecarriedout to gain insights into this peculiar reactivity (Figure 4).The reactionb egins with the double reductiono fC S 2 by complex 1,y ielding the dinuclear "key intermediate" (complex 3). This step was found to be exothermic by 22.4 kcal mol À1 as foundi no ther reactions.…”

“…CS 2 activation by lanthanide ions has so far resulted in CS 2 disproportionation or reductive C−S or C−C coupling to afford thiocarbonate, thiooxalate and thioformyl carbonotrithioate [(SCSCS 2 ) 2− ] respectively . Very recently the first example of a rare CS 2 2− dianion trapped between two Yb III ions has also been reported …”

“…[8] Very recently the first example of ar are CS 2 2À dianion trapped between two Yb III ions has also been reported. [9] CO reductivec oupling by samarium(II) and uranium(III) complexesh as been reported to afford ketene carboxylate and ynediolate OÀCCÀO 2À (which act as linear k 2 -O,O' bridging ligands), respectively. [10] In contrast, the formation of the acetylenedithiolate dianion analogue (SÀCCÀS) 2À from CS 2 or CS reductionh as never been reported.…”

“…Hydrogen atoms, methyl groups, and co-crystallized 3 wereomitted for clarity.Selected bond lengths (): C1BÀC2B = 1.16(4);C1BÀS1B = 1.71(2); C2BÀS2B = 1.72(2);Yb1ÀS1B = 2.566(6);Yb2ÀS2B = 2.664(6). Hydrogen atoms and methylgroups were omitted for clarity.S electedb ond lengths (): C1AÀS1 = 1.673 (18);C1AÀS2 = 1.68(2), Yb1ÀS1 = 2.656(4);Y b2À S2 = 2.645(5);Yb1ÀC1A = 2.52(2); Yb2ÀC1A = 2.531 (17). other reported lanthanide complex of CS 2 2À [Yb 2 (DippForm) 4 (CS 2 )] [9] (m-h 3 (S,C,S'):h 2 (S,C)) or in the U IV complexes, [U({OSi(OtBu) 3 } 3 ) 2 (m-CS 2 )], [4b] [mh 2 (S,C):h 2 (S,S')] and [(CH 3 C 5 H 4 ) 3 U] 2 (m-CS 2 )], [4a] [(mh 2 (S,C):h 1 (S')] isolatedf rom the reduction of CS 2 by two mononuclear Yb II and U III complexes, respectively.O nly two examples of dinuclear complexesp resenting as imilars ymmetrical coordination mode with two side-on bound C-S fragments have been reported so far for d-block metals. [2c, 3c] The complexes 2 and 3 co-crystallizea nd could not be isolated separately for analyticalp urposes, but they can be isolated together in good yield from the other reaction products by crystallization.…”