Direct electrochemical synthesis of benzenethiolato complexes of tin(II), tin(IV) and lead(II). The molecular structure of the 2,2'-bipyridine adduct of Sn(SC6H5)4

Structural studies of organoboron compounds. XVII.' Preparation and crystal and molecular structure of 3a-methyl-2,4,9a-triphenyl-1,2,3a,4,9,9a-hexahydro-1,3,9-trioxa-3a-azonia-2-bora-9a-boratacyclopenta Thc titlc compound was prepared by the reaction of 8-mcthyl-6.6-diphenyI-5,7-dioxa-8-azonia-6-borata-6.7-dihydro-5H-benzocycloheptene (1) with phenylboronic acid. Crystals of 3n-methyl-2.4,9o-triphcnyl-I,2,3n,4,9,9n-hexahydro-1,3,9-trioxa-3a-azonia-2-bora-9a-boratacyclopenta[b]naphthalene are monoclinic. a = 1 I .8548(4), b = 22.7837(4), c = 8.5457 (3) A, P = 106.952(2)", Z = 4, space group P21/n. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.040 and R,,. = 0.047 for 2970 reflections with I 2 3u(I). The molecule was found to bc a formal addition product between 1 and PhBO which had undergone a 1.4-shift of a phenyl group from boron to carbon. The backbone of thc molecule consi:ts of a folded system of three fuscd rings. The structure contains thc longest known B(. On a prtpard le compost mentionnt dans le titre en faisant rdagir de I'acide phtnylboronique avec le mdthyl-8 diphdnyl-6,6 dioxa-5,7 azonia-8 borata-6 dihydro-6.7 5H-benzocyclohept~ne ( I ) . Les cristaux du mkthyl-3a triphtnyl-2,4,9n hexahydro-1 ,2,3a34,9,9n trioxa-1,3,9 a~onia-30 bora-2 borata-90 cyclopcnta [b]naphtalene sont monocliniques, a = 1 1,8548(4), b = 22,7837(4), c = 8,5457(3) A, P = 106,952(2)", Z = 4, groupe d'espace P2,lrl. On a rdsolu la structure par des mtthodes directes et on l'a affinee par la mtthode des moindres carrts (matrices completes) jusqu'a des valeurs de R = 0,040 et R,.. = 0,047 pour 2970 rtflexions avec I 2 3u(I). On a trouvt que la moltcule est le produit d'addition forinelle entre 1 et PhBO qui a subi une transposition 1.4 du groupement phtnyle du bore au carbone. La base de la moltcule comporte un qystkme replik de trois cycles condensks. La structure comporte la liaison B(.sp3)-~(s~.') la plus longue connue, 1.759(2) A . [Traduit par le journal]

Section: The 22'-bipyridinium Cation and The [Bpyh)supporting

confidence: 92%

Structural studies of organoboron compounds. XVII. Preparation and crystal and molecular structure of 3a-methyl-2,4,9a-triphenyl-1,2,3a,4,9,9a-hexahydro-1,3,9-trioxa-3a-azonia-2-bora-9a-boratacyclopenta[b]naphthalene

Kliegel¹,

Nanninga²,

Rettig³

et al. 1984

“…g refs. [9][10][11][12]. W e could find no previous mention of dissolution of these thiolates in the presence of excess thiolate ion or of characterization of the soluble species so formed.…”

mentioning

confidence: 99%

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)

Arsenault¹,

Dean²

1983

. 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) ...

“…The method of preparing these new compounds was essentially the same as those used in our previous papers (1)(2)(3)(4)(5)(6)(7)(8)(9)(10). The solution phase was contained in a 100 mL round-bottomed flask with a Schlenk arm; a metal rod suspended through rubber septum formed the anode of the cell, and a platinum wire was the cathode.…”

Section: Electrochemical Synthesismentioning

confidence: 99%

The direct electrochemical synthesis of d¹⁰ metal ion derivatives of some anionic bidentate oxygen donors

Annan¹,

Peppe²,

Tuck³

1990

Self Cite

. Can. J. Chem. 68, 423 (1990).The electrochemical oxidation of a sacrificial anode (M = Zn, Cd, Hg, In, Sn) in non-aqueous solutions of 3-hydroxyflavone, 1'-hydroxy-2'-acetonaphthone, or 2-ethoxyphenol (= HL) gives ZnL2, CdL2, HgL, InL3, or SnL2 (not all combinations).Adducts with 2,2'-bipyridine (bpy) or N,N,N1,N'-tetramethylethanediamine (tmen) have also been prepared in some cases.Certain zinc and cadmium compounds produce paramagnetic species on exposure to the atmosphere. The structure of Zn(C15H903)2tmen has been deter@ned; the crystals are orthorhombic, space group Pbcn, cell dimensions a = 18.8 17 (2) Mots clis : synthkses klectrochimiques, ions mktalliques dl0, diffraction des rayons-X, complexe du zinc, complexe du cadmium.[Traduit par la revue] I