Divergent reactivity of an indole glucosinolate yields Lossen or Neber rearrangement products: the phytoalexin rapalexin A or a unique ß-d-glucopyranose fused heterocycle.

Transformation of 1-t-Boc-4-methoxyindole-3-glucosinolate under acidic conditions yielded the potent phytoalexin rapalexin A, providing its first biomimetic synthesis via Lossen type rearrangement, while a novel 1-thioimidocarbonyl-ß-d-glucopyranose heterocyclic system was obtained under basic conditions via Neber type rearrangement.

Preparation, crystal structure, and spectroscopic characterization of [(Se(2)SN(2)Cl](2).

The reaction of [(Me(3)Si)(2)N](2)S with an equimolar amount of SeCl(4) in dioxane at 50 degrees C affords [(Se(2)SN(2))Cl](2) (1) in excellent yield. Crystals of 1 are orthorhombic, space group Pbca, with a = 8.5721(7) A, b = 7.8336(6) A, c = 15.228(1) A, and Z = 8. The crystal structure contains two planar Se(2)SN(2)(*)(+) rings which are linked by intermolecular Se.Se interactions [d(Se-Se) = 3.0690(7) A]. The EI mass spectrum shows Se(2)SN(2)(*)(+) as the fragment of highest mass. Both the (14)N and (77)Se NMR spectra show a single resonance (-52 and 1394 ppm, respectively). The solid [(Se(2)SN(2))Cl](2) gives a strong ESR signal indicating the presence of a Se(2)SN(2)(*)(+) radical. The Raman spectrum was assigned through normal coordinate treatment involving a general valence force field. The vibrational analysis yielded a good agreement between the observed and calculated wavenumbers.

Preparation and x-ray structures of alkali-metal derivatives of the ambidentate anions [tBuN(E)P(mu-NtBu)2P(E)NtBu]2- (E = S, Se) and [tBuN(Se)P(mu-NtBu)2PN(H)tBu)]-.

The ambidentate dianions [(t)BuN(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu](2)(-) (5a, E = S; 5b, E = Se) are obtained as their disodium and dipotassium salts by the reaction of cis-[(t)Bu(H)N(E)P(mu-N(t)Bu)(2)P(E)N(H)(t)Bu] (6a, E = S; 6b, E = Se), with 2 equiv of MN(SiMe(3))(2) (M = Na, K) in THF at 23 degrees C. The corresponding dilithium derivative is prepared by reacting 6a with 2 equiv of (t)BuLi in THF at reflux. The X-ray structures of five complexes of the type [(THF)(x)()M](2)[(t)BuN(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu] (9, M = Li, E = S, x = 2; 11a/11b, M = Na, E = S/Se, x = 2; 12a, M = K, E = S, x = 1; 12b, M = K, E = Se, x = 1.5) have been determined. In the dilithiated derivative 9 the dianion 5a adopts a bis (N,S)-chelated bonding mode involving four-membered LiNPS rings whereas 11a,b and 12a,b display a preference for the formation of six-membered MNPNPN and MEPNPE rings, i.e., (N,N' and E,E')-chelation. The bis-solvated disodium complexes 11a,b and the dilithium complex 9 are monomeric, but the dipotassium complexes 12a,b form dimers with a central K(2)E(2) ring and associate further through weak K.E contacts to give an infinite polymeric network of 20-membered K(6)E(6)P(4)N(4) rings. The monoanions [(t)Bu(H)N(E)P(mu-N(t)Bu)(2)P(E)N(t)Bu)](-) (E = S, Se) were obtained as their lithium derivatives 8a and 8b by the reaction of 1 equiv of (n)BuLi with 6a and 6b, respectively. An X-ray structure of the TMEDA-solvated complex 8a and the (31)P NMR spectrum of 8b indicate a N,E coordination mode. The reaction of 6b with excess (t)BuLi in THF at reflux results in partial deselenation to give the monolithiated P(III)/P(V) complex [(THF)(2)Li[(t)BuN(Se)P(mu-N(t)Bu)(2)PN(H)(t)Bu]] 10, which adopts a (N,Se) bonding mode.

Preparation and X-ray structures of Cu(I), Ni(II), and Pd(II) (N,S) complexes of the monoanion [(tBuN)(S)P(mu-N(t)Bu)2P(S)(NH(t)Bu)]- and a Pt(II) (S,S') complex of the dianion [((t)BuN)(S)P(mu-N(t)Bu)2P(S)(N(t)Bu)]2-.

The metathetical reactions of the lithium derivative of the monoanion [((t)BuN)(S)P(mu-N(t)Bu)(2)P(S)(NH(t)Bu)](-) (L) with CuCl/PPh(3), NiCl(2)(PEt(3))(2), PdCl(2)L'(2) (L' = PhCN, PPh(3)), and PtCl(2)(PEt(3))(2) produced the complexes (PPh(3))CuL (5), NiL(2) (6), PdCl(L)(PPh(3)) (7), PdL(2) (8), and Pt(PEt(3))(2)[((t)BuN)(S)P(mu-N(t)Bu)(2)P(S)(N(t)Bu)] (9). The X-ray structures of 5, 6, and 8 reveal a N,S-coordination for the chelating monoanion L with the metal centers in trigonal planar, tetrahedral, and square planar environments, respectively. By contrast, the dianionic ligand in the square planar Pt(II) complex 9 is S,S'-chelated to the metal center. (31)P NMR spectra readily distinguish between the N,S and S,S' bonding modes, and, on that basis, N,S chelation is inferred for the Pd(II) complex 7. Crystal data: 5, monoclinic, P2(1)/c, a = 19.175(4) A, b = 20.331(4) A, c = 10.017(6) A, beta = 91.79(3) degrees, V = 3903(2) A(3), and Z = 4; 6, orthorhombic, Pbcn, a = 14.298(5) A, b = 15.333(5) A, c = 24.378(5) A, beta = 90.000(5) degrees, V = 5344(3) A(3), and Z = 4; 8, monoclinic, P2(1)/n, a = 13.975(3) A, b = 14.283(3) A, c = 15.255(4) A, beta = 116.565(18) degrees, V = 2723.5(11) A(3), and Z = 2; 9, monoclinic, P2(1)/n, a = 12.479(6) A, b = 21.782(7) A, c = 17.048(5) A, beta = 100.30(3) degrees, V = 4559(3) A(3), and Z = 4.

Lithium halide adducts of imidotellurium(IV) ligands: synthesis and X-ray structures of [Li(THF)2L](mu 3-I)[LiI(L)] [L = tBuNTe(mu-NtBu)2TeNtBu] and [(THF)3Li3(mu 3-I)(Te(NtBu)3)].

The reaction of the chelating ligand tBuNTe(mu-NtBu)2TeNtBu (L) with LiI in THF yields [Li(THF)2L](mu 3-I)[LiI(L)] (3). This complex is also formed by the attempted oxidation of [Li2Te(NtBu)3]2 with I2. An X-ray analysis of 3 reveals that the tellurium diimide dimer acts as a chelating ligand toward (a) [Li(THF)2]+ cations and (b) a molecule of LiI. An extended structure is formed via weak Te...I interactions [3.8296(7)-3.9632(7) A] involving both mu 3-iodide counterions and the iodine atoms of the coordinated LiI molecules. Crystal data: 3, triclinic, space group P1, a = 10.1233(9) A, b = 15.7234(14) A, c = 18.8962(17) A, alpha = 86.1567(16) degrees, beta = 84.3266(16) degrees, gamma = 82.9461(16) degrees, V = 2965.8(5) A3, Z = 2. The oxidation by air of [Li2Te(NtBu)3]2 in toluene produces the radical (Li3[Te(NtBu)3]2), which exhibits an ESR spectrum consisting of a septet of decuplets (g = 2.00506, a(14N) = 5.26 G, a(7Li) = 0.69 G). The complexes [(THF)3Li3(mu 3-X)(Te(NtBu)3)] (4a, X = Cl; 4b, X = Br; 4c, X = I) are obtained from the reaction of [Li2Te(NtBu)3]2 with lithium halides in THF. The iodide complex, 4c, has a highly distorted, cubic structure comprised of the pyramidal [Te(NtBu)3]2- dianion which is linked through three [Li(THF)]+ cations to I- Crystal data: 4c, triclinic, space group P1, a = 12.611(8) A, b = 16.295(6) A, c = 10.180(3) A, alpha = 98.35(3) degrees, beta = 107.37(4) degrees, gamma = 108.26(4) degrees, V = 1829(2) A3, Z = 2.

Tetraaza analogues of lithium and sodium alums: synthesis and X-ray structures of the single strand polymer [Li(THF)2(Al[SO2(NtBu)2]2)] infinity and the contact ion pairs [Na(15-crown-5)][Al(SO2(NtBu)2)2] and ([Na(15-crown-5)][O2S(mu-NBn)2Al(mu-NBnSO2NBn)])2.

The reaction of an alkali metal aluminohydride MAlH4 (M = Li, Na) with N,N'-bis-(tert-butyl)sulfamide or N,N'-bis-(benzyl)sulfamide in THF produces the complex ions (Al[SO2(NR)2]2)- (R = tBu, Bn). The X-ray structures of [Li(THF)2(Al[SO2(NtBu)2]2)] infinity (1), [Na(15-crown-5)][Al(SO2(NtBu)2)2], (2) and ([Na(15-crown-5)][O2S(mu-NBn)2Al(mu-NBnSO2NBn)])2 (3.3THF) are reported. The two diazasulfate ligands [SO2(NtBu)2]2- are N,N' chelated to Al3+ in both 1 and 2. In the lithium derivative 1 the spirocyclic (Al[SO2(NtBu)2]2)- anions are bridged by the bis-solvated cations Li(THF)2+ to give a polymeric strand. In the sodium salt 2 the complex anion is O,O' chelated to Na+, which is further encapsulated by a 15-crown-5 ligand to give a monomeric ion-pair complex. By contrast, the benzyl derivative 3 forms a dimer in which the terminal [SO2(NBn)2]2- ligands are (N,N'),(O,O') bis-chelated to Al3+ and Na+, respectively, and the bridging ligands adopt a novel N,O-chelate, N'-monodentate bonding mode. The central core of 3 consists of two four-membered AlOSN rings bridged by two NtBu groups. Crystal data: 1, orthorhombic, Pna2(1), a = 20.159(5) degrees, b = 10.354(3) degrees, c = 15.833(4) degrees, alpha = beta = gamma = 90 degrees, V = 3304.7(15) A3, Z = 4; 2, monoclinic, P2(1)/n, a = 16.031(2) A, b = 9.907(2) A, c = 23.963(4) A, beta = 103.326(2) degrees, Z = 4; 3, triclinic, P1, a = 12.7237(11) A, b = 14.0108(13) A, c = 16.2050(14) A, alpha = 110.351(2) degrees, beta = 111.538(2) degrees, gamma = 97.350(2) degrees, Z = 1.

Synthesis and characterization of [ButNSn(mu-NBut)2TeNBut](mu3-SnTe), a stannanetellurone with four-coordinate tin.

Treatment of [Li2Te(NBut)3]2 with Sn(O3SCF3)2 or SnCl2 in diethyl ether generates the stannanetellurone [ButNSn(mu-NBut)2 TeNBut](mu3-SnTe) involving four-coordinate tin with d(Sn=Te) = 2.589(1) A; the two Sn and two Te atoms are in different oxidation states (+II/+IV and +IV/-II, respectively).

Steric effects on the mode of aggregation and reactivity of clusters formed from the lithiation of trisamidothiophosphates.

Lithiation of SP[N(H)R]3 with LiBun produces the dimers [(THF)LiSP(NR)(NHR)2]2 (R = Pri) or ([LiSP(NR)-(NHR)2][(THF)LiSP(NR)2(NHR)])2 (R = But) with central Li2N2 or Li2S2 rings, respectively; further lithiation yields the dianion [SP(NR)2(NHR)]2- (R = Pri) or leads to sulfur extrusion when R = But.

Selenium imides: 77Se NMR investigations of the SeCl2-tBuNH2 reaction and X-ray structures of Se3(NtBu)3, tBuNSe(mu-NtBu)2SO2, and tBuNSe(mu-NtBu)2SeO.

The reaction of SeCl2 with tert-butylamine in various molar ratios in THF at -78 degrees C has been investigated by 77Se NMR spectroscopy. In addition to the known Se-N heterocycles Se6(NtBu)2 (1) and Se9(NtBu)6 (2), the acyclic imidoselenium(II) dichlorides ClSe[N(tBu)Se]nCl (4, n = 1; 5, n = 2) and two new cyclic selenium imides [Se3(NtBu)2]n (3, n = 1 or 2) and Se3(NtBu)3 (6) have been isolated and identified. An X-ray analysis shows that 6 is a six-membered ring in a chair conformation with magnitude of d(Se-N) = 1.833 A. Crystal data: 6, trigonal, P3c1, a = 9.8660(3) A, c = 20.8427(7) A, V = 1757.0(1) A3, Z = 6. The 1H, 13C, and 77Se NMR data for 1-6 are reported, and some reassignments of earlier literature data for 1-3 (n = 1) are made. The decomposition of tBuN=Se=NtBu at 20 degrees C in toluene was monitored by 77Se NMR. The major products are 6 and 3. The Se(IV)-N systems tBuNSe(mu-NtBu)2E (7, E = SO2; 8, E = SeO) were prepared by the reaction of a mixture of SeCl4 and excess tBuNH2 with SO2Cl2 or SeOCl2, respectively. Compound 8 is also generated by the cycloaddition reaction of tBuNSeNtBu with tBuNSeO. Both 7 and 8 consist of slightly puckered four-membered rings. The mean terminal and bridging Se-N distances in 7 are 1.665(2) and 1.948(2) A, respectively. The corresponding values for 8 are 1.687(4) and 1.900(4) A, and d(Se=O) = 1.628(4) A. Crystal data: 7, monoclinic, P2(1)/c, a = 18.669(4) A, b = 12.329(2) A, c = 16.463(3) A, beta = 115.56(3) degrees, V = 3418.4(11) A3, Z = 4; 8, triclinic, P1, a = 6.372(1) A, b = 9.926(2) A, c = 14.034(3) A, alpha = 99.320(3) A, beta = 95.764(3) A, gamma = 103.876(3) A, V = 841.3(3) A3, Z = 2.

Coinage Metal Complexes of a Tellurium Diimide: cis-->trans Isomerization and Metal-Metal Interactions.

The different coordination behavior of the ligand tBuN=Te(µ-NtBu)(2)Te=NtBu (L) towards Cu(+) and Ag(+) results from a cis-->trans isomerization. The two Cu(+) ions in [Cu(2)L(3)](2+) (shown schematically) bridge trans and cis isomers of the ligand, whereas the Ag(+) ions in [Ag(2)L(2)](2+) link two trans ligands and exhibit a weak Ag small middle dot small middle dot small middle dotAg interaction.