Reactions of (η⁵-C₅Me₅)Ir(PMe₃)(SH)₂and (η⁵-C₅Me₅)Ir(PMe₃)(SH)(H) with Thionylaniline (PhNSO) to Give Novel Iridium S₃O and S₂O Complexes

Abstract

Treatment of Cp*Ir(PMe3)(SH)2 (1), where Cp* = η5-C5Me5, with thionylaniline (PhNSO), CS2, and p-tolylisothiocyanate (p-tolNCS) gave Cp*Ir(PMe3)(S3O) (3), Cp*Ir(PMe3)(S2CS) (4), and Cp*Ir(PMe3)(SH)(SC(S)HN-p-tol) (5), respectively. Treatment of Cp*Ir(PMe2R)(H)(SH) (2a,b), where R = Me (2a), Ph (2b), with PhNSO gave Cp*Ir(PMe2R)(S2O) (6a,b) as mixtures of interconvertible conformational isomers. Treatment of 2a with p-tolNCS gave Cp*Ir(PMe3)(H)(SC(S)NH-p-tol) (7). The crystal structures of 3−5, 6b, and 7 are reported.

CC Bond Formation through Reductive Coupling of CS2 to Yield Uranium Tetrathiooxalate and Ethylenetetrathiolate Complexes

“…In accordance with a two-electron reduction process, the bond order increases to a C=C double bond as indicated in the C55ÀC55' bond of 1.383 (8) that is comparable to reported ethylenetetrathiolate complexes. [13,16,17] The C55 À S1 and C55 À S2 bond lengths (1.789(4) and 1.766(4) ) in 3 and longer than in 2 and in other ethylenetetrathiolate complexes (ca.…”

“…Generation of trithiocarbonate complexes from CS 2 has been well-documented. [8][9][10] However, the formation of C 2 S 4 nÀ units from the reductive coupling of CS 2 is uncommon [11][12][13][14][15][16][17] despite C 2 S 4 ligands being implicated as the conducting units in multimetallic complexes. [18][19][20] Unlike dianionic C 2 O 4 2À…”

Accurate Structure and Bonding Description of the Transition Metal‐Disulfur Monoxide Complexes [(PMe3)2M(S2O)] (M = Ni, Pd, Pt): Grimme Dispersion Corrected DFT Study

“…The first example of the disulfur monoxide complex [(dppe)Ir(S 2 O)]Cl was reported by Schmid and co‐workers 7. The field has been expanded with well characterized examples of disulfur monoxide complexes of Nb,8 Mo,9–12 Re,13 Rh,7 Mn,13–16 Os,17 Ir,6,7,18 and Pt 19–21 . Ishii and co‐workers have reported the structure and properties of platinum‐S 2 O complex [(Ph 3 P) 2 Pt(S 2 O)] 21.…”

“…The X‐ray crystal structure of this complex is not very clear, having disordered Pt(S 2 O) moieties (Figure S1 in Supporting Information). Shaver and co‐workers reported an iridium complex [Cp*(PMe 3 )Ir(S 2 O)], in which they represent the existence of two isomeric forms of metal‐S 2 O bonding, i.e., exo and endo modes 18. Structurally characterized transition metal‐disulfur monoxide complexes and their important structural parameters are presented in Table 1.…”

C‐C‐Bindungsknüpfung durch reduktive Kupplung von CS2 an Uran zur Bildung von Tetrathiooxalat‐ und Ethylentetrathiolatkomplexen

“…Schon seit längerem ist bekannt, dass mit CS 2 Trithiocarbonatkomplexe hergestellt werden können. [8][9][10] Die Bildung von C 2 S 4 nÀ -Einheiten durch reduktive Kupplung von CS 2 ist allerdings ungewöhnlich, [11][12][13][14][15][16][17] obschon verbrückende C 2 S 4 -Einheiten eine wichtige Rolle in elektrisch leitenden Multimetallkomplexen spielen. [18][19][20] Im Unterschied zum dianionischen C 2 O 4 2À kann C 2 S 4 nÀ verschiedene Oxidationsstufen annehmen, die vom tetraanionischen Ethylentetrathiolat (C 2 S 4…”