Bis(diethyldithiocarbamato)(iodo)(4-methoxyphenyl)tellurium(IV), \u3cem\u3ep\u3c/em\u3e-MeOC\u3csub\u3e6\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3eTe(Et\u3csub\u3e2\u3c/sub\u3eNCS\u3csub\u3e2\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3eI, and its Isomorphous Partially Bromine-Replaced Analogue, \u3cem\u3ep\u3c/em\u3e-MeOC\u3csub\u3e6\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3eTe(Et\u3csub\u3e2\u3c/sub\u3eNCS\u3csub\u3e2\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3eBr\u3csub\u3e0.41\u3c/sub\u3eI\u3csub\u3e0.59\u3c/sub\u3e

The structure of the title TeIV complex, C13H19BrN2OS4Te.045(CH2Cl2), is pentagonal bipyramidal with four S atoms [Te-S 2.623 (1)-2.717 (1) Å] and the Br atom [Te-Br 2.890 (1) Å] in equatorial positions. The p-methoxyphenyl group is axial [Te-C 2.145 (3) Å] and the second axial position seems to be occupied by a dithiocarbamate group of a neighbouring molecule acting as a -ligand [TeC 3.751 (3) Å, C-TeC 170.2 (1)°], so that molecules are joined into centrosymmetric associations by this secondary coordination

\u3cem\u3eN\u3c/em\u3e-Methylbenzothiazole-2(3\u3cem\u3eH\u3c/em\u3e)-selone, C\u3csub\u3e8\u3c/sub\u3eH\u3csub\u3e7\u3c/sub\u3eNSSe

The crystal structure of N-methyl1,3-benzothiazole-2(3H)-selone, (mbts) has been studied to estimate the changes in the molecular geometry of the mbts ligand upon coordination. Hypervalent complexes of mbts with TeII and II have been studied by us previously. A significant elongation of the Se=C bond [from 1.817 (7) in mbts to 1.85-1.88 Å in the complexes] was found, but there were no significant changes in the other geometric parameters of the ligand. The only other bond-length decrease of note was for SeC-NMe [from 1.35 (1) in mbts to 1.32-1.34 Å in the complexes]. Thus, only the amino group takes part in electron redistribution upon coordination

\u3cem\u3ecis\u3c/em\u3e-(Diethyldithiocarbamato)diiodo(phenyl)tellurium(IV), PhTe(S\u3csub\u3e2\u3c/sub\u3eCNEt\u3csub\u3e2\u3c/sub\u3e)I\u3csub\u3e2\u3c/sub\u3e, and its Methoxy-Substituted Mixed Br/1 Analogue \u3cem\u3ecis\u3c/em\u3e-Bis(0.4-bromo/0.6-iodo)-(diethyldithiocarbamato)(4-methoxyphenyl) tellurium(IV), \u3cem\u3ep\u3c/em\u3e-MeOC\u3csub\u3e6\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3eTe(S\u3csub\u3e2\u3c/sub\u3e CNEt\u3csub\u3e2\u3c/sub\u3e)(Br\u3csub\u3e0.4\u3c/sub\u3eI\u3csub\u3e0.6\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3e

The TeIV complexes PhTe(S2CNEt2)I2, (1), and p-MeOC6H4Te(S2CNEt2)Br0.4/I0.6) 2, (2), have been synthesized by reacting PhTeI3 with NaS2CNEt2, and p-MeOC6H4Te(S2CNEt2)2I with Br2, respectively. In (2), both I atoms are partially replaced by Br atoms in a 3:2 ratio. The structures display distorted octahedral Te coordination with two symmetrically coordinated S atoms [Te—S 2.550 (2)—2.569 (2) Å in three independent molecules of (1) and 2.523 (1) Å in (2)] and with two cis-disposed halogen atoms [Te—I 2.941 (1)—2.986 (1) Å in (1) and 3.003 (4) and 3.049 (3) Å in (2); Te—Br 2.962(8) and 2.967 (8) Å in (2)] in equatorial positions. The aryl group is axial in both complexes [Te—C 2.137(6)—2.146(6) and 2.123(5) Å in (1) and (2) respectively] and the second axial position is occupied by a halogen atom of a neighbouring molecule [Te⋅⋅⋅I 3.898(1)—4233(1) Å in (1); Te⋅ ⋅ ⋅I3872(3) Å and Te⋅ ⋅ ⋅Br 3.676(6) Å in (2); trans angles C---Te⋅ ⋅ ⋅ (Br) 153.4(2)—177.7(2)°] so that the molecules are joined into (quasi)centrosymmetric pairs by these secondary interactions

Bromobis(Diethyldithiocarbamato)(4-Methoxyphenyl)Tellurium(IV)

The crystals of the TeIV complex p-CH3OC6H4Te(Et2NCS2)2Br are isomorphous with those of the the iodine and mixed iodine/bromine analogues previously investigated. The structure is pentagonal bipyramidal at the Te atom with four S atoms [Te-S 2.618-2.721 (1) Å] and the Br atom [Te-Br 2.943 (1) Å] in equatorial positions. The p-methoxyphenyl group is axial [Te-C 2.147 (3) Å]. The second axial position is approached by a Br atom of a centrosymmetrically related complex [TeBr 3.423 (1) Å, C-TeBr 173.1 (1)°] so that the molecules are joined into centrosymmetric pairs by this weak secondary coordination

Multisteroid LC-MS/MS assay for glucocorticoids and androgens, and its application in Addison’s disease

Objective: Liquid chromatography–tandem mass spectrometry (LC–MS/MS) offers superior analytical specificity compared with immunoassays, but it is not available in many regions and hospitals due to expensive instrumentation and tedious sample preparation. Thus, we developed an automated, high-throughput LC–MS/MS assay for simultaneous quantification of ten endogenous and synthetic steroids targeting diseases of the hypothalamic–pituitary–adrenal axis and gonads. Methods: Deuterated internal standards were added to 85 μl serum and processed by liquid–liquid extraction. Cortisol, cortisone, prednisolone, prednisone, 11-deoxycortisol, dexamethasone, testosterone, androstenedione and progesterone were resolved by ultra-high-pressure chromatography on a reversed-phase column in 6.1 min and detected by triple-quadrupole mass spectrometry. The method was used to assess steroid profiles in women with Addison's disease (AD, n=156) and blood donors (BDs, n=102). Results: Precisions ranged from 4.5 to 10.1% relative standard deviations (RSD), accuracies from 95 to 108% and extraction recoveries from 60 to 84%. The method was practically free of matrix effects and robust to individual differences in serum composition. Most postmenopausal AD women had extremely low androstenedione concentrations, below 0.14 nmol/l, and median testosterone concentrations of 0.15 nmol/l (interquartile range 0.00–0.41), considerably lower than those of postmenopausal BDs (1.28 nmol/l (0.96–1.64) and 0.65 nmol/l (0.56–1.10) respectively). AD women in fertile years had androstenedione concentrations of 1.18 nmol/l (0.71–1.76) and testosterone concentrations of 0.44 nmol/l (0.22–0.63), approximately half of those found in BDs of corresponding age. Conclusion: This LC–MS/MS assay provides highly sensitive and specific assessments of glucocorticoids and androgens with low sample volumes and is suitable for endocrine laboratories and research. Its utility has been demonstrated in a large cohort of women with AD, and the data suggest that women with AD are particularly androgen deficient after menopause.publishedVersio

μ-OXO-BIS[TRIS(PYRROLIDINO-N)PHOSPHONIUM] TRIFLUOROMETHANESULFONATE, A SALT WITH A DIPHOSPHONIUM ION WITH A NON-LINEAR P[sbnd]O[sbnd]P SEQUENCE

The title compound contains the diphosphonium ion, [(C4H8N)3P[sbnd]O[sbnd]P(NC4H8)3]2+. The structure of the compound is disordered at room temperature. By slow cooling, it goes through a phase transition near −100°C and as a result becomes ordered. Unlike the similar cations [(Me2N)3P[sbnd]O[sbnd]P(NMe2)3]2+, and [(OC4H8N)3P[sbnd]O[sbnd]P(NC4H8O)3]2+, it has a non-linear P[sbnd]O[sbnd]P sequence both in the disordered and ordered phase with P[sbnd]O[sbnd]P angles between 155.5(3) and 159.2(3)°. The X-ray crystallographic study of the title compound, both at 273 and 103 K, shows that the P[sbnd]O and P[sbnd]N bond lengths are very similar to those of the linear cations. The P[sbnd]O and P[sbnd]N bond lengths in the title compound ranges from 1.578(4) to 1.602(4) Å and from 1.585(5) to 1.605(5) Å, respectively

Tautomeric Conversion of a Thiourea Ligand upon Formation of a Hypervalent Tellurium (II) Complex. Synthesis, and X-ray Structural Studies of N-Phenyl-N’-(1,3-Thiazol-2-YL)-Thiourea and Bromophenyl [1-Phenyl-3-(1’,3’-Thiazol-3’-ium-2’-YL)-isothioureidato]tellurium

The divalent tellurium title complex (II) has been synthesized by addition of Ph2Te2 and Br2 to the ligand 1-phenyl-3-(2-thiazolyl)-2-thiourea (I).The molecular structures of I and II were subsequently determined by X-ray crystallographic methods. As a result, it was found that upon complexation, the ligand had undergone a transition from a thiourea to to an isomeric isothiourea, involving a transfer of a thiourea proton to the thiazolyl ring. This does not seem to influence the bonding properties of the ligand, and the reasons for this are discussed. The central tellurium atom is three-coordinate and its coordination sphere is T-shaped with a linear S-Te-Br sequence with bond lengths Te(1)-S(1) and Te(1)-Br(1) equal to 2.548(1) and 2.883(1) Å, respectively, and ∠ S(1)-Te(1)-Br(1)=174.49(2)°. At nearly right angles to this sequence, there is a Te(1)-C(11)(phenyl) bond of 2.127(3) Å

Synthesis and structural characterization of [Te{(SePPh₂)₂N}₂] and [4-MeOPhTe{(SPPh₂)₂N}]₂

Reaction of K[(SePPh2)2N] with [Te(tu)4]Cl2 (tu = thiourea) in methanol gave [Te{(SePPh2)2N}2], (1), while reaction of K[(SPPh2)2N] with 4-MeOPhTeCl3 in methanol gave [4-MeOPhTe-{(SPPh2)2N}]2, (2). The crystals of 1 are triclinic and contain centrosymmetric molecules. The ligands are bidentate and form a true square planar Te(II) complex with TeSe4 coordination. For 2, the crystals are also triclinic, and the dimeric molecules are centrosymmetric. Each dithiolate ligand bridges the two Te(II) atoms; the result is a T-shaped coordination around each tellurium atom. A tendency to weak Te-Te bonding across the ring-formed dimer roughly in the direction of the missing fourth ligand in a potential square planar tellurium coordination sphere is also found [Te-Te = 3.761 (1) Å]. In 1, the Te-Se bonds have an average length of 2.797 Å. The Te-S bonds in 2 are quite asymmetric with Te(1)-S(1) = 2.551 (3) Å and Te(1)-S(2a) = 2.873 (3) Å, while Te(1)-C(1) = 2.10 (1) Å.</p