Polygenic loading for major depression is associated with specific medical comorbidity.

Major depressive disorder frequently co-occurs with medical disorders, raising the possibility of shared genetic liability. Recent identification of 15 novel genetic loci associated with depression allows direct investigation of this question. In cohorts of individuals participating in biobanks at two academic medical centers, we calculated polygenic loading for risk loci reported to be associated with depression. We then examined the association between such loading and 50 groups of clinical diagnoses, or topics, drawn from these patients' electronic health records, determined using a novel application of latent Dirichilet allocation. Three topics showed experiment-wide association with the depression liability score; these included diagnostic groups representing greater prevalence of mood and anxiety disorders, greater prevalence of cardiac ischemia, and a decreased prevalence of heart failure. The latter two associations persisted even among individuals with no mood disorder diagnosis. This application of a novel method for grouping related diagnoses in biobanks indicate shared genetic risk for depression and cardiac disease, with a pattern suggesting greater ischemic risk and diminished heart failure risk.

Psychological interventions to reduce suicidality in high-risk patients with major depression: a randomized controlled trial.

BACKGROUND: Positive psychological constructs have been associated with reduced suicidal ideation, and interventions to cultivate positive feelings have the potential to reduce suicide risk. This study compares the efficacy of a 6-week, telephone-based positive psychology (PP) intervention against a cognition-focused (CF) control intervention among patients recently hospitalized for depression and suicidal ideation or behavior. METHOD: A total of 65 adults with a current major depressive episode reporting suicidal ideation or a recent suicide attempt were enrolled from participating in-patient psychiatric units. Prior to discharge, participants were randomized to the PP (n = 32) or CF (n = 33) intervention. In both interventions, participants received a treatment manual, performed weekly PP (e.g. gratitude letter) or CF (e.g. recalling daily events) exercises, and completed weekly one-on-one telephone sessions over 6 weeks. Between-group differences in hopelessness (primary outcome), depression, suicidality and positive psychological constructs at 6 and 12 weeks were tested using mixed-effects models accounting for intensity of post-hospitalization psychiatric treatment. RESULTS: Compared with PP, the CF intervention was associated with significantly greater improvements in hopelessness at 6 weeks (ß = -3.15, 95% confidence interval -6.18 to -0.12, effect size = -0.84, p = 0.04), but not 12 weeks. Similarly, the CF intervention led to greater improvements in depression, suicidal ideation, optimism and gratitude at 6 and 12 weeks. CONCLUSIONS: Contrary to our hypothesis, the CF intervention was superior to PP in improving hopelessness, other suicide risk factors and positive psychological constructs during a key post-discharge period among suicidal patients with depression. Further study of this CF intervention is warranted in populations at high suicide risk.

Rapid screening for major depression in post-myocardial infarction patients: an investigation using Beck Depression Inventory II items.

OBJECTIVE: To determine the ability of three questions from the Beck Depression Inventory II (BDI-II) to detect major depressive disorder (MDD) in a cohort of patients hospitalised for acute myocardial infarction (MI). DESIGN: Prospective observational study. SETTING: Coronary care unit and cardiac step-down unit of an urban academic medical centre. PATIENTS: 131 post-MI patients within 72 h of symptom onset. INTERVENTIONS: Patients were administered the BDI-II and participated in a structured diagnostic interview for MDD. Three individual BDI-II items (regarding sadness, loss of interest and loss of pleasure) were examined individually and in two-question combinations to determine their ability to screen for MDD. MAIN OUTCOME MEASURES: Sensitivity, specificity, negative and positive predictive values and proportion of patients with MDD correctly identified. RESULTS: The individual items and two-question combinations had good sensitivity (76-94%), specificity (70-88%) and negative predictive values (97-99%). Item 1 (sadness) performed the best of the individual items (48% with a positive response to the item had MDD; 3% with a negative response had MDD; over 80% of patients with MDD were correctly identified). A combination of questions about sadness and loss of interest performed best among the two-question combinations (37% with positive response had MDD v 1% with a negative response; 94% of patients with MDD were identified). CONCLUSIONS: One to two questions regarding sadness and loss of interest serve as simple and effective screening tools for post-MI depression.

Facile C(sp(2))/OR bond cleavage by Ru or Os.

Os(H)(3)ClL(2) (L = P(i)Pr(3) or P(t)Bu(2)Me) are shown to be useful "precursors" to "OsHClL(2)", which react with vinyl ethers to form first an eta(2)-olefin adduct and then isomerize to the carbenes, OsHCl[CMe(OR)]L(2). Subsequent R- and L-dependent reactions involve C(sp(2))-OR bond cleavage, to make either carbyne or vinylidene complexes. The mechanisms of these reactions are explored, and the thermodynamic disparity of Ru versus Os and the influence of the OR group and the spectator phosphine ligands are discussed based on DFT (B3PW91) calculations.

Effect of Lewis acidity on the synthesis of RuHCl(CO)(phosphine)(2): subtle influence of steric and electronic effects among P(i)Pr(3), P(i)Pr(2)(3,5-(CF(3))(2)C(6)H(3)), and P(i)Pr(2)Me.

To evaluate the influence of steric, electronic, and synthetic factors, the synthesis of RuHCl(CO)[P(i)Pr(2)(3,5-(CF(3))(2)C(6)H(3))](2) was carried out, and its Lewis acidity toward Cl- was compared to that of RuHCl(CO)(P(i)Pr(3))(2). In this synthesis, Na(2)CO(3) was shown to be a more effective base than NEt(3), because Na+ can better mask the nucleophilicity of the potential ligand Cl-. An X-ray structure determination of the hydride-free species RuCl(2)(CO)(P(i)Pr(2)Me)(2) shows it to be a dimer, and this solid-state structure persists in solution, but as several different isomers. The synthesis of RuHCl(CO)(P(i)Pr(2)Me)(3) shows that three of this smaller phosphine can crowd around Ru, but dynamic NMR spectra show one phosphine to be weakly bound. The rate of reaction of Me(3)SiC(triple bond)CH with this molecule is suppressed by added free P(i)Pr(2)Me, indicating phosphine dissociation to be a mechanistic component.

Synthesis and reactivity of silyl vinylketenes: a formal interrupted Dötz benzannulation with unexpected silyl migration.

[reaction: see text]. An efficient method for the generation of silyl vinylketenes from the thermal reaction of Fischer carbene complexes with silyl-substituted phenylacetylenes is described. Although the silyl vinylketene products are highly stable, conditions have been identified to induce a benzannulation/silyl migration process, providing aromatic silyl ethers.

A comparison of the influences of alkoxide and thiolate ligands on the electronic structure and reactivity of molybdenum(3+) and tungsten(3+) complexes. preparation and structures of M(2)(O(T)Bu)(2)(S(t)Bu)(4), [Mo(S(t)Bu)(3)(NO)](2), and W(S(t)Bu)(3)(NO)(py).

M(2)(O(t)Bu)(6) compounds (M = Mo, W) react in hydrocarbon solvents with an excess of (t)BuSH to give M(2)(O(t)Bu)(2)(S(t)Bu)(4), red, air- and temperature-sensitive compounds. (1)H NMR studies reveal the equilibrium M(2)(O(t)Bu)(6) + 4(t)BuSH <==> M(2)(O(t)Bu)(2)(S(t)Bu)(4) + 4(t)BuOH proceeds to the right slowly at 22 degrees C. The intermediates M(2)(O(t)Bu)(4)(S(t)Bu)(2), M(2)(O(t)Bu)(3)(S(t)Bu)(3), and M(2)(O(t)Bu)(5)(S(t)Bu) have been detected. The equilibrium constants show the M-O(t)Bu bonds to be enthalpically favored over the M-S(t)Bu bonds. In contrast to the M(2)(O(t)Bu)(6) compounds, M(2)(O(t)Bu)(2)(S(t)Bu)(4) compounds are inert with respect to the addition of CO, CO(2), ethyne, (t)BuC triple bond CH, MeC triple bond N, and PhC triple bond N. Addition of an excess of (t)BuSH to a hydrocarbon solution of W(2)(O(t)Bu)(6)(mu-CO) leads to the rapid expulsion of CO and subsequent formation of W(2)(O(t)Bu)(2)(S(t)Bu)(4). Addition of an excess of (t)BuSH to hydrocarbon solutions of [Mo(O(t)Bu)(3)(NO)](2) and W(O(t)Bu)(3)(NO)(py) gives the structurally related compounds [Mo(S(t)Bu)(3)(NO)](2) and W(S(t)Bu)(3)(NO)(py), with linear M-N-O moieties and five-coordinate metal atoms. The values of nu(NO) are higher in the related thiolate compounds than in their alkoxide counterparts. The bonding in the model compounds M(2)(EH)(6), M(2)(OH)(2)(EH)(4), (HE)(3)M triple bond CMe, and W(EH)(3)(NO)(NH(3)) and the fragments M(EH)(3), where M = Mo or W and E = O or S, has been examined by DFT B3LYP calculations employing various basis sets including polarization functions for O and S and two different core potentials, LANL2 and relativistic CEP. BLYP calculations were done with ZORA relativistic terms using ADF 2000. The calculations, irrespective of the method used, indicate that the M-O bonds are more ionic than the M-S bonds and that E ppi to M dpi bonding is more important for E = O. The latter raises the M-M pi orbital energies by ca. 1 eV for M(2)(OH)(6) relative to M(2)(SH)(6). For M(EH)(3) fragments, the metal d(xz)(),d(yz)() orbitals are destabilized by OH ppi bonding, and in W(EH)(3)(NO)(NH(3)) the O ppi to M dpi donation enhances W dpi to NO pi* back-bonding. Estimates of the bond strengths for the M triple bond M in M(2)(EH)(6) compounds and M triple bond C in (EH)(3)M triple bond CMe have been obtained. The stronger pi donation of the alkoxide ligands is proposed to enhance back-bonding to the pi* orbitals of alkynes and nitriles and facilitate their reductive cleavage, a reaction that is not observed for their thiolate counterpart.

Single-molecule magnets: preparation and properties of mixed-carboxylate complexes.

Methods are reported for the preparation of mixed-carboxylate versions of the [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(4)] family of single-molecule magnets (SMMs). [Mn(12)O(12)(O(2)CCHCl(2))(8)(O(2)CCH(2)Bu(t))(8)(H(2)O)(3)] (5) and [Mn(12)O(12)(O(2)CHCl(2))(8)(O(2)CEt)(8)(H(2)O)(3)] (6) have been obtained from the 1:1 reaction of the corresponding homocarboxylate species. Complex 5.CH(2)Cl(2).H(2)O crystallizes in the triclinic space group P1 with, at -165 degrees C, a = 15.762(1), b = 16.246(1), c = 23.822(1) A, alpha = 103.92(1), beta = 104.50(1), gamma = 94.23(1) degrees, Z = 2, and V = 5674(2) A(3). Complex 6.CH(2)Cl(2) crystallizes in the triclinic space group P1 with, at -158 degrees C, a = 13.4635(3), b = 13.5162(3), c = 23.2609(5) A, alpha = 84.9796(6), beta = 89.0063(8), gamma = 86.2375(6) degrees, Z = 2, and V = 4207.3(3) A(3). Complexes 5 and 6 both contain a [Mn(12)O(12)] core with the CHCl(2)CO(2-) ligands ordered in the axial positions and the RCO(2-) ligands (R = CH(2)Bu(t) (5) or Et (6)) in equatorial positions. There is, thus, a preference for the CHCl(2)CO(2-) to occupy the sites lying on the Mn(III) Jahn-Teller axes, and this is rationalized on the basis of the relative basicities of the carboxylate groups. Direct current magnetic susceptibility studies in a 10.0 kG field in the 2.00-300 K range indicate a large ground-state spin, and fitting of magnetization data collected in the 10.0-70.0 kG field and 1.80-4.00 K temperature range gave S = 10, g = 1.89, and D = -0.65 K for 5, and S = 10, g = 1.83, and D = -0.60 K for 6. These values are typical of [Mn(12)O(12)(O(2)CR)(16)(H(2)O)(4)] complexes. Alternating current susceptibility studies show the out-of-phase susceptibility (chi(M)' ') signals characteristic of the slow relaxation in the millisecond time scale of single-molecule magnets. Arrhenius plots obtained from chi(M)' ' versus T data gave effective barriers to relaxation (U(eff)) of 71 and 72 K for 5 and 6, respectively. (1)H NMR spectra in CD(2)Cl(2) show that 5 and 6 are the main species present on dissolution, but there is evidence for some ligand distribution between axial and equatorial sites, by intra- and/or intermolecular exchange processes.

Assessment and understanding of pain in patients with dementia.

The literature on pain in dementia patients is reviewed. A summary of methods for assessment of pain in demented elderly persons and an examination of studies that used such methods are included. In addition, literature theorizing a decrease in affective pain in this population is discussed; management of pain in such patients is not discussed extensively. Research reveals 3 major findings: (a) a moderate decrease in pain occurs in cognitively impaired elderly persons, (b) communicative dementia patients' reports of pain tend to be as valid as those of cognitively intact patients, and (c) assessment scales developed thus far for noncommunicative patients require improvement in accuracy and facility. Many questions about pain in dementia patients remain, and the continued development of valid pain assessment techniques is a necessity.

A new class of electron-rich unsaturated molecules: Ru2HnX4-n(PiPr3)4, X = anion.

Synthesis, spectroscopic, and X-ray structural characterization of Ru2HnCl4-nL4 (n = 2, 3) and Ru2H2F2L4 (L = PiPr3) are reported. The structure of Ru2HCl3L4 is also reported. These are dinuclear species containing two five-coordinate, approximately square-pyramidal metal atoms. Halides, not hydrides, preferentially occupy bridging sites, and the RuXL2 terminal moiety shows limited fluxionality, but hydrides do not migrate between metals. The limited steric protection provided by PiPr3 is evident from the dimerization observed and from the fact that all these structures have rather small [symbol: see text]P-Ru-P (approximately 105 degrees). Also reported are RuHXL2 species with X = acetylacetonate, phenoxide, O3SCH3, and O3SCF3. Several examples of coordinated olefin to complexed carbene conversions are used to test the influence of anion X on reactivity.

Dimolybdenum bis((S,S,S)-triisopropanolaminate(3-)): a blue compound with an unusual Mo-Mo triple bond.

Mo2(OtBu)6 and Mo2(NMe2)6 each react with (S,S,S)-triisopropanolamine (2 equiv) in benzene to yield dimolybdenum bis((S,S,S)-isopropanolaminate(3-)), Mo2[(OC-(S)-HMeCH2)3N]2 (M identical to M), as a blue crystalline solid. Cell parameters at -160 degrees C: a = 17.389(6) A, b = 10.843(3) A, c = 10.463(3) A, beta = 125.28(1) degrees, Z = 2 in space group C2. The molecular structure involves an Mo2 unit inside an O6N2 distorted cubic box. The Mo2 axis is disordered about three positions with occupancy factors of ca. 45%, 45%, and 10%. Despite this disorder, the molecular structure is shown to contain a central Mo identical to Mo unit of distance 2.15(3) A coordinated to two triolate ligands which each have two chelating arms and one that spans the Mo identical to Mo bond. The local Mo2O6N2 moiety has approximate C2h symmetry, and the Mo-N distances are long, 2.4 A. The 1H and 13C(1H) NMR spectra recorded in benzene-d6 are consistent with the geometry found in the solid-state structure. The blue color arises from weak absorptions, epsilon approximately 150 dm3 mol-1 cm-1, at 580 and 450 nm in the visible region of the electronic absorption spectrum. Raman spectra recorded in KCl reveal pronounced resonance effects with excitation wavelengths of 488.0, 514.5, and 568.2 nm, particularly for the 322 cm-1 band, which can probably be assigned to nu(Mo identical to Mo). The electronic structure of this compound is investigated by B3LYP DFT calculations, and a comparison is made with the more typical ethane-like (D3d) Mo2(OR)6 compounds is presented. The distortion imposed on the molecule by the triisopropanolaminate(3-) ligands removes the degeneracy of the M-M pi molecular orbitals. The HOMO and SHOMO are both M-M pi and M-O sigma* in character, while the LUMO is M-M pi* and the SLUMO is predominantly M-O sigma* with metal sp character. The calculated singlet-singlet transition energies are compared with those implicit in the observed electronic spectrum.

Single-molecule magnets: a new class of tetranuclear manganese magnets.

The preparation, X-ray structure, and detailed physical characterization are presented for a new type of single-molecule magnet [Mn4(O2CMe)2(pdmH)6](ClO4)2 (1). Complex 1.2MeCN.Et2O crystallizes in the triclinic space group P1, with cell dimensions at 130 K of a = 11.914(3) A, b = 15.347(4) A, c = 9.660(3) A, alpha = 104.58(1) degree, beta = 93.42(1) degree, gamma = 106.06(1) degree, and Z = 1. The cation lies on an inversion center and consists of a planar Mn4 rhombus that is mixed-valent, MnIII2MnII2. The pdmH- ligands (pdmH2 is pyridine-2,6-dimethanol) function as either bidentate or tridentate ligands. The bridging between Mn atoms is established by either a deprotonated oxygen atom of a pdmH- ligand or an acetate ligand. The solvated complex readily loses all acetonitrile and ether solvate molecules to give complex 1, which with time becomes hydrated to give 1.2.5H2O. Direct current and alternating current magnetic susceptibility data are given for 1 and 1.2.5H2O and indicate that the desolvated complex has a S = 8 ground state, whereas the hydrated 1.2.5H2O has a S = 9 ground state. Ferromagnetic interactions between MnIII-MnII and MnIII-MnIII pairs result in parallel spin alignments of the S = 5/2 MnII and S = 2 MnIII ions. High-frequency EPR spectra were run for complex 1.2.5H2O at frequencies of 218, 328, and 436 GHz in the 4.5-30 K range. A magnetic-field-oriented polycrystallite sample was employed. Fine structure is clearly seen in this parallel-field EPR spectrum. The transition fields were least-squares-fit to give g = 1.99, D = -0.451 K, and B4 degrees = 2.94 x 10(-5) K for the S = 9 ground state of 1.2.5H2O. A molecule with a large-spin ground state with D < 0 can function as a single-molecule magnet, as detected by techniques such as ac magnetic susceptibility. Out-of-phase ac signals (chi'' M) were seen for complexes 1 and 1.2.5H2O to show that these complexes are single-molecule magnets. A sample of 1 was studied by ac susceptibility in the 0.4-6.4 K range with the ac field oscillating at frequencies in the 1.1-1000 Hz range. A single peak in chi'' M vs temperature plots was seen for each frequency; the temperature of the chi'' M peak varies from 2.03 K at 995 Hz to 1.16 K at 1.1 Hz. Magnetization relaxation rates were evaluated in this way. An Arrhenius plot gave an activation energy of 17.3 K, which, as expected, is less than the 22.4 K value calculated for the thermodynamic barrier for magnetization direction reversal for an S = 8 complex with D = -0.35 K. The 1.2.5H2O complex with an S = 9 ground state has its chi'' M peaks at higher temperatures.

Unsaturated Ru(0) species with a constrained bis-phosphine ligand: [Ru(CO)2(tBu2PCH2CH2PtBu2)]2. Comparison to [Ru(CO)2(PtBu2Me)2].

The synthesis of Ru(C2H4)(CO)2(dtbpe) (dtbpe = tBu2PC2H4PtBu2), then green [Ru(CO)2(dtbpe)]n is described. In solution, n = 1, while in the solid state, n = 2; the dimer has two carbonyl bridges. DFTPW91, MP2, and CCSD(T) calculations show that the potential energy surface for bending one carbonyl out of the RuP2C(O) plane is essentially flat. Ru(CO)2(dtbpe) reacts rapidly in benzene solution to oxidatively add the H-E bond of H2, HCl, HCCR (R = H, Ph), [HOEt2]BF4, and HSiEt3. The H-C bond of C6HF5 oxidatively adds at 80 degrees C. CO adds, as does the C=C bond of H2C=CHX (X = H, F, Me). The following do not add: N2, THF, acetone, H3COH, and H2O.

Behavioral disturbances in geropsychiatric inpatients across dementia types.

The objective of this study was to compare differences in behavioral, psychiatric, and cognitive status among geropsychiatric inpatients with Alzheimer's, vascular, alcohol-induced, and mixed dementia. Participants included 150 patients with dementia consecutively admitted to an acute geropsychiatric inpatient unit. Measures included the Mini-Mental State Examination, Cohen-Mansfield Agitation Inventory, Cumulative Illness Rating Scale, Basic and Independent Activities of Daily Living, Positive and Negative Syndrome Scale for Schizophrenia, and the Initiation/Perseveration subscale of the Dementia Rating Scale. No significant differences existed in the character or severity of agitation among patients with Alzheimer's, vascular, alcohol-related and mixed dementia. Interestingly, patients with vascular dementia compared to patients with other dementias admitted for behavioral disturbances were less cognitively impaired and more medically burdened.

Tetranuclear manganese carboxylate complexes with a trigonal pyramidal metal topology via controlled potential electrolysis.

Controlled potential electrolysis (CPE) procedures are described that provide access to complexes with a [Mn4(mu 3-O)3(mu 3-O2CR)]6+ core (3MnIII,MnIV) and a trigonal pyramidal metal topology, starting from species containing the [Mn4(mu 3-O)2]8+ core (4MnIII). [Mn4O2(O2CMe)6(py)2(dbm)2] (6): triclinic, P1, a = 10.868(3) A, b = 13.864(3) A, c = 10.625(3) A, alpha = 108.62(1) degrees, beta = 118.98(1) degrees, gamma = 89.34(2) degrees, V = 1307 A3, Z = 1, T = -131 degrees C, R (Rw) = 3.24 (3.70)%. [Mn4O2(O2CPh)6(py)(dbm)2] (8): monoclinic, P2(1)/c, a = 14.743(6) A, b = 15.536(8) A, c = 30.006(13) A, beta = 102.79(1) degrees, V = 6702 A3, Z = 4, T = -155 degrees C, R (Rw) = 4.32 (4.44)%. Both 6 and 8 contain a [Mn4O2]8+ core; 8 only has one py group, the fourth MnIII site being five-coordinate. (NBun4)[Mn4O2(O2CPh)7(dbm)2] (10) is available from two related procedures. CPE of 10 at 0.65 V vs ferocene in MeCN leads to precipitation of [Mn4O3(O2CPh)4(dbm)3] (11); similarly, CPE of 6 at 0.84 V in MeCN/CH2Cl2 (3:1 v/v) gives [Mn4O3(O2CMe)4(dbm)3] (12). Complex 11: monoclinic, P2(1)/n, a = 15.161(3) A, b = 21.577(4) A, c = 22.683(5) A, beta = 108.04(3) degrees, V = 7056 A3, Z = 4, T = -100 degrees C, R (wR2) = 8.63 (21.80)%. Complex 12: monoclinic, P2(1)/n, a = 13.549(2) A, b = 22.338(4) A, c = 16.618(2) A, beta = 103.74(1) degrees, V = 4885 A3, Z = 4, T = -171 degrees C, R (Rw) = 4.63 (4.45)%. Both 11 and 12 contain a [Mn4(mu 3-O)3(mu-O2CR)] core with a Mn4 trigonal pyramid (MnIV at the apex) and the RCO2- bridging the MnIII3 base. However, in 11, the carboxylate is eta 2,mu 3 with one O atom terminal to one MnIII and the other O atom bridging the other two MnIII ions, whereas in 12 the carboxylate is eta 1,mu 3, a single O atom bridging three MnIII ions. Variable-temperature, solid-state magnetic susceptibility studies on 11 and 12 show that, for both complexes, there are antiferromagnetic exchange interactions between MnIII/MnIV pairs, and ferromagnetic interactions between MnIII/MnIII pairs. In both cases, the resultant ground states of the complex is S = 9/2, confirmed by magnetization vs field studies in the 2.00-30.0 K and 0.50-50 kG temperature and field ranges, respectively.

Structural distortions in mer-M(H)3(NO)L2 (M = Ru, Os) and their influence on intramolecular fluxionality and quantum exchange coupling.

Molecules of the type mer-M(H)3(NO)L2 [M = Ru (1), Os (2); L = PR3] are characterized on the basis of 1H NMR T1min values and IR spectra as pseudo-octahedral trihydrides significantly distorted by compression of the cis H-M-H angles to approximately 75 degrees. The distortion, uncharacteristic of six-coordinate d6 complexes, is rationalized with DFT (B3LYP) calculations as being driven by increased H-to-M sigma donation and by the exceptional pi-accepting ability of linear NO+. In both 1 and 2, hydrides undergo intramolecular site exchange with delta HHH++(1) = 10-11 kcal/mol and delta HHH++(2) = 16-20 kcal/mol, depending on L, whereas for mer-Ru(H)3(NO)(PtBu2Me)2 (1b), moderate exchange couplings (up to 77 Hz) are featured in the low-temperature 1H NMR spectra, in addition to chemical exchange. On the basis of experimental and theoretical results, a dihydrogen intermediate is suggested to mediate hydride site exchange in 1. The cis H-M-H distortion shortens the tunneling path for the exchanging hydrides in 1, thereby increasing the tunneling rate; diminishes the "conflict" between trans hydrides in the mer geometry; and decreases the nucleophilicity of the hydrides. The generality of the observed structural distortion and its dependence on the ligand environment in late transition metal tri- and dihydrides are discussed. A less reducing metal center is generally characterized by greater distortion.

Non-quassinoid constituents from the twigs and thorns of Castela polyandra.

The structures of two new constituents, a beta-glycoside (1) and a steroid (2), isolated from the twigs and thorns of Castela polyandra, were established by a combination of spectroscopic and single-crystal X-ray analysis.