A <sup>31</sup>P nuclear magnetic resonance spectroscopic study of complexes of cadmium(II) with some phosphine oxides, sulfides, and selenides

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31P nmr has been used to show that, in MeNO2, M(SbF6)2 (M = Sn or Pb) forms 1:1 complexes with Ph2P(CH2)2PPh2, PhP[(CH2)2PPh2]2, MeC(CH2PPh2)3, [Formula: see text][Formula: see text]P[(CH2)2PPh2]3, and Ph2P[(CH2)2PPh]2(CH2)2PPh2. The phosphonium ligands are formed in situ. Spectra characteristics of slow inter- and intramolecular exchange were obtained in all cases except, perhaps, those involving the last two ligands, which may be involved in rapid intramolecular exchange. For the first five ligands, the maximum denticity is achieved and unambiguous one-bond M(II)—31P (M = 117/119Sn or 207Pb) coupling constants are reported and discussed. In the presence of M(SbF6)2 (M = Sn or Pb). PPh3 is protonated in MeNO2, while in acetone Sn(SbF6)2 forms a 1:1 complex with PPh3 which appears to be solvent-inserted, [Sn—O—CMe2PPh3]2+.Reduced temperature 31P nmr spectroscopy has allowed the detection of 1:2 and 1:3 (M:L) complexes of OPPh3, and 1:1 complexes of Ph2P(O)(CH2)2P(O)Ph2, PhP(O)[(CH2)2P(O)Ph2]2, and (O)P[(CH2)2P(O)Ph2]3, with both tin(II) and lead(II). The 1:1 complexes with polydentate ligands are isolable; nmr shows that the maximum denticity occurs except with the last ligand which behaves in a tridentate manner. Several two-bond M—O—P coupling constants have been obtained. Also, the changes which complexation produces in the P—P couplings are compared with changes produced in the analogous phosphine complexes.The synthesis and characterization of Ph2P(E)[(CH2)2P(E)Ph]2(CH2)2P(E)Ph2 (E = S or Se) and (Se)P[(CH2)2P(Se)Ph2]3 are reported. The 31P nmr spectra of these compounds are compared with those of the parent tetraphosphines and other members of the corresponding tetraoxide–tetrachalcogenide series.

“…Several of the phosphine oxides were prepared as part of an earlier study (18). PP304 (19) was prepared using 12/OH-, as previously.…”

Section: Methodsmentioning

confidence: 99%

A ³¹P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the ³¹P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

Dean¹,

Phillips²,

Polensek³

1981

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“…In addition, combined "'Cd and j'P nnlr spectroscopic scri~tiny of c a d n l i~~n l c o nplexes of phosphine oxides, sulfides. and selenides (3)(4)(5) has shown these to be useful models lor the ""d nmr chemical…”

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

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. 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) ...

“…Our intention was to establish a series of related complexes of Group VIA donor ligands in which the kernel could be varied methodically, so providing a basis for a "'Cd nmr study in which the effect of systematic change about the cadmium could be investigated. There is general agreement on the need for more and better model compound studies to advance the plexes we characterized earlier (1,2). Unambiguous slow exchange l13Cd spectra have been observed, allowing us to assess the effect on the " T d resonance of change of donor atom only, change in ligation number only, change of substituents on the phosphorus atom of the phosphine chalcogenides, and change in the number and size of chelate rings in six-coordinate complexes of chelating phosphine oxides.…”

Section: Introductionmentioning

confidence: 78%

“…double distillation in a nitrogen atmosphere. The literature routes (16) to Cd(AsF,), and Cd(SbF,), were used to prepare the In this paper we present "3Cd Ilmr for salts containing ";Cd in natural abundance, and the preparaselected members from among the cadmium corn-tions of the ligands, except OP(C,H,,),, have been given earlier also (1,2,17 …”

Section: Experimental Cklaterialsmentioning

confidence: 99%

“…Previously, we have used reduced temperature 31P nmr to characterize, in SO, solution, a wide range of cadmium complexes with phosphine oxides, sulfides, or selenides, as well as some mixtures of these, as ligands (1,2). Our intention was to establish a series of related complexes of Group VIA donor ligands in which the kernel could be varied methodically, so providing a basis for a "'Cd nmr study in which the effect of systematic change about the cadmium could be investigated.…”

Section: Introductionmentioning

confidence: 99%

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A ¹¹³Cd nuclear magnetic resonance study of some complexes of cadmium with phosphine oxides, sulfides, and selenides

Dean¹

1981

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113Cd(AsF6)2 has been synthesized from 113CdO by treatment in SO2 with PF5 then AsF5. From the 113Cd-enriched salt have been prepared [Cd(EPR3)4]2+ (E = O, R = C6H11; E = S or Se, R = Ph), [Cd(SP(C6H11)3)x(SeP(C6H11)n−x]2+ (n = 4, x = 0–4; n = 3, x = 0–3), [Cd(EP(o-C6H4Me)3)n]2+ (E = S, n = 4 or 2; E = Se, n = 3 or 2), [Cd(Ph2P(O)(CH2)nP(O)Ph2)3]2+ (n = 1 or 2), and [Cd(Ph2P(O)((CH2)2P(O)Ph2)2)2]2+ in liquid SO2. The reduced temperature slow exchange 31P and 113Cd nmr spectra have been measured and are discussed. The 31P nmr are as expected from previous work on complexes containing 113Cd at natural abundance except that several values of 2J(113Cd—O—31P) have been measured. From the 113Cd spectra the most important shielding sequences observed are [Formula: see text] for [Cd(EP(C6H11)3)4]2+, δ2:1 < δ3:1 < δ4:1 for [Cd(EPR3)n]2+ (E = S or Se, n = 1–4, constant R), and [Formula: see text] for the various phosphine oxide complexes studied.The synthesis of SO2-insoluble Cd(SbF6)2•3(OP(C6H11)3) is reported.