A preparative and multinuclear nuclear magnetic resonance spectroscopic study of As(SPh)_x(SePh)_3−x(x = 0−3), Sb(SPh)_x(SePh)_3−x (x = 0−3), Bi(SPh)₃, Bi(SePh)₃, [Sn(SPh)_x(SePh)_3−x]⁻(x = 0−3), Pb(SePh)₃⁻, and Pb(SPh)₃⁻ and some related thiolatoplumbates(II)

Abstract

. Can. J. Chcm. 61. 1516Chcm. 61. (1983. The phenyl sclcnolatcs of tin(ll), Icad(l1). arscnic(lll), antirnony(lll), and bismuth(l1l). M(ScPh),, (M = Sn(ll) or Pb(ll), rr = 2; M = As(ll1). Sb(ll1). or Bi(lll), rr = 3). have been synthcsizccl by acid-base reaction of the appropriate metal acetate (for M = Sn(ll) or Pb(ll)) or thiophcnolatc (for all five clcmcnts) with PhScH. and characterized by clcrncntal analysis and, for the Group V elcmcnts, 77Sc and I3C nnir spectroscopy.M(SPh), and M(ScPh): (M = Sn(l1) or Pb(ll)) arc poorly solublc in McOH but dissolve in the presence of an equimolar or greater amount of P h S or P h S c . The solublc st;unnatc(ll) con~plcxcs arc triligatccl as shown by the slow exchange I1"Sn and, where appropriate. 7 7~c nmr spcctra of the series [Sn(SPh),(ScPh), , I (.r = 0-3) mcasurcd for the supernatant liquor of mixtures in which {Sn(EPh)l),,,,,,l/Pl~E -,,,,;,I > I . The corresponding plumbatc(ll) complcxcs arc pr-obably triligatcd also, but are labile on the nmr timcscalc; the parent complexes P b ( E P h ) havc bccn chmctcrizcd in solution by "I7pb and I3C (E = S and Sc) and 7 7~c (E = Sc) nmr spectroscopy. For both Pb(l1) and Sn(ll), the orclcr of chcmical shifts in the rnctal nmr spcctra is G(MSc3) > 6(MS,). The metal nmr spcctra of the mixturcs M(ScPh),:PhSc :PhS = 1 : 2 : 4 (M = Sn(ll) or Pb(ll)) show that the coordination of P h S c occurs in prcfcrcncc to coordination of P h S fo~. both tin(l1) and Icatl(l1).Thiolatoplurnbatcs(l1) might bc formed during somc antidotal treatments for lead poisoning, so "fingerprint" 2 " 7~b nmr spcctra havc bccn mcasurcd for a rangc of model s o l~~b l c spccics formed in Pb(SR),-(cxccss)RS mixturcs in McOH, including somc mixturcs containing newly synthcsizcd and characterized lead thiolatcs derived from dithiolatc unions. For RS-= MeS-, E t S . PhS-, C h H l l S -(for which "Pb(SR)Z" has bccn shown to bc Pb(SC,Hl1)(OAc)), S ( C H Z ) , S / 2 , -SCH,CHSMc/2. and -SCH,CHS C H~O H ' , 61.1, (from PbMc, in toluene as rcfcrcncc) falls in the conlparativcly short rangc 25 18-2999 pprn.The redistribution of ligands bctwccn M(SPh)> and M(ScPh), in chloroform to give cquilibsium mixtures of M(SPh),(SePh),..., occurs slowly on the preparative timcscalc for M = As, rapidly on the prcp~u.ativc timcscalc but slowly on the "C and 77Sc nmr timcscales for M = Sb, and rapidly on the ' C and 77Sc 111iir tinlcscalcs for M = Bi. Thus 13C and, where appropriate, 7 7~c nnlr data arc reported for M(SPh),(ScPh),+, (M = As or Sb) and Bi(EPh)> ( E = S or Sc). In addition, it has been possible, using I3C nmr assessment of spccics distribution in the systems Sb(SPh),-As(ScPh) and Bi(SPh)3-As(ScPh),, to dcducc that for the trivalent Group V clemcnts the ordcr of prcfcrcncc for PhSc-over PhS-as ligands is Bi > Sb > As.Trends in the I3C nmr data for M ( s P h ) . , ( s~P h )~ , (M = As or Sb) and 77Sc nnlr data for a rangc of metal complcxcs of PhSchavc been discussed. The sclcniurn chemical shifts arc influcnccd primarily by the acceptor atom and asc in the ordcr Cd(ll) ...

Probing a Homoleptic PbS3 Coordination Environment in a Designed Peptide Using 207Pb NMR Spectroscopy: Implications for Understanding the Molecular Basis of Lead Toxicity

“…The coordination number and geometry of the Pb 2+ ion can also be examined 29. Dean, Payne, Christou, and their co‐workers have synthesized [Ph 4 As][Pb(SPh) 3 ] and characterized complexes in non‐aqueous media using 207 Pb NMR spectroscopy 30–32. Despite these studies, no significant advancement of 207 Pb NMR has been accomplished to explore the thiolate‐rich proteins scaffolds.…”

1‐D‐Tin(II) Phenylchalcogenolato Complexes ∞1[Sn(EPh)2] (E = S, Se, Te) – Synthesis, Structures, Quantum Chemical Studies and Thermal Behaviour

“…Synthetic procedures for compounds with the general formula Sn(ER) 2 (E = S, Se, Te; R = organic group) are especially for thiolato complexes well established. With respect to the compounds under investigation Sn(SPh) 2 13–16 as well as Sn(SePh) 2 17 have been synthesized before while no report could be found for the tellurium analogue. However the structures of only a few compounds of this type are reported including monomeric [Sn(S‐2,4,6‐ t C 4 H 9 C 6 H 2 ) 2 ],18 dimeric [Sn{TeSi(SiMe 3 ) 3 } 2 ] 2 12 and [Sn(2‐SeNC 5 H 4 ) 2 ] 2 ,11 trimeric [Sn(S‐2,6‐( i C 3 H 7 ) 2 C 6 H 3 ) 2 ] 3 as well as polymeric ∞ 1 [Sn(S t C 4 H 9 ) 2 ]19 and ∞ 1 [Sn(S n C 4 H 9 ) 2 ] 20.…”

Solution and Solid-State Characterization of PbSe Precursors

“…This might be due to an exchange of coordinating ethylenediamine ligands that is faster than the NMR timescale. Nonobservance of the lead signal has been reported for mixed ligand species of PhSe –1 and PhS –1 for lead complexes by Dean . Similarly, Rekken et al did not observe a lead signal for their lithium tristhiolato plumbate (LiPb­(SAr Me6 ) 3 ) complex …”