Evaluation of sleep quality, insomnia severity and OSAS risk in primary care population: A descriptive study.

PURPOSE: In our study, we aimed to evaluate the sleep quality, insomnia presence and severity, obstructive sleep apnoea syndrome (OSAS) risk of the patients who applied to family health centres and to determine the situations that might be related with these features. METHODS: This study is a descriptive research and conducted in Ankara Güdül, Antalya Degirmenözü, Bursa Sirameseler, Gaziantep Family Health Centre policlinics. The study population consisted of all patients over 18 years of age who were admitted to the family health centres for any reason. A 10-question questionnaire, Berlin questionnaire, Pittsburgh sleep quality questionare and insomnia severity questionare were applied by the researchers from October to December 2017 by using face-to-face interview method. RESULTS: Two hundred nineteen nine people participated in study and 54.5% of them were women. According to the results of Pittsburgh Sleep Quality Questionare, it was found that 27.1% of the participants' sleep quality was good; according to the Berlin sleep questionnaire, 27.4% of the participants had high OSAS risk. According to Insomnia Severity Questionare, 27.1% of them had insomnia lower threshold, 15.4% had moderate insomnia and 3.7% severe insomnia. CONCLUSIONS: In this context, it will be very effective in terms of the quality of life of patients in order to determine the conditions that disrupt sleep hygiene and to perform the necessary interventions which can be intervened in the primary healthcare institutions and the other patients to be delivered to the related upper levels.

Borabicyclo[3.2.0]heptadiene: A Fused Bicyclic Isomer of Borepin.

A new isomer of borepin, identified as 2-borabicyclo[3.2.0]hepta-3,6-diene by single-crystal X-ray diffraction and heteronuclear NMR spectroscopy, was obtained by reaction of 1-mesityl-2,3,4,5-tetraphenylborole with the diaminoalkyne bis(piperidyl)acetylene. Analogous reactions of the alkyne with other borole derivatives generated seven-membered borepins, in which a second equivalent of the alkyne was found to insert into the exocyclic B-C bond. Results of mechanistic DFT studies as well as differences in the reactivity of the boroles toward the diaminoalkyne are discussed.

Scope of the Thermal Ring-Expansion Reaction of Boroles with Organoazides.

Electronic and steric factors have been investigated in the thermal ring expansion of boroles with organic azides, a reaction that provides access to highly arylated 1,2-azaborinines, BN analogues of benzene. Reactions of a variety of boroles and organic azides demonstrate that the synthetic method is quite general in furnishing 1,2-azaborinines, but the respective reaction rates reveal a strong dependence on the substituents on the two reactants. The products have been characterized by UV/Vis, electrochemical, NMR, and X-ray diffraction methods, clarifying their constitutions and highlighting substituent effects on the electronic structure of the 1,2-azaborinines. Furthermore, analysis of several possible mechanistic pathways for 1,2-azaborinine formation, as studied by DFT, revealed that a two-step mechanism involving azide-borole adduct formation and nitrene insertion is favored.

Reactivity of a Dihydrodiborene with CO: Coordination, Insertion, Cleavage, and Spontaneous Formation of a Cyclic Alkyne.

Under a CO atmosphere, the dihydrodiborene [(cAAC)HB=BH(cAAC)] underwent coordination of CO concomitant with reversible hydrogen migration from boron to the carbene carbon atom, as well as reversible CO insertion into the B=B bond. Heating the CO adduct resulted in two unusual cAAC ring-expansion products, one presenting a B=C bond to a six-membered 1,2-azaborinane-3-ylidene, the other an unprecedented nine-membered cyclic alkyne resulting from reductive cleavage of CO and spontaneous formation of a C≡C bond.

From Borane to Borylene without Reduction: Ambiphilic Behavior of a Monovalent Silylisonitrile Boron Species.

Deprotonation of [(cAAC)BH2 (CN)] provided clean access to the stable boryl anion, [(cAAC)BH(CN)]- . Whereas the addition of soft electrophiles occurred at the nucleophilic boron center, harder silyl electrophiles added to the harder terminal cyano nitrogen. The resulting [(cAAC)BH(CNSiPh3 )] species behaved like a silylium boryl nucleophile as well as a neutral silylisonitrile borylene.

Boron-Metallated Borirenes and Bis(Borirenes).

Heating the metalloborylene complex [{(η(5) -C5 Me5 )Fe(CO)2 }(µ-B){Cr(CO)5 }] with alkynes and diynes leads to the formation of B-metallated borirenes and a bis(B-metallated borirene) through formal transfer of the metalloborylene moiety [(η(5) -C5 Me5 )(OC)2 Fe(B:)]. By using this protocol, a range of B-metallated borirenes with electron-donating and electron-withdrawing substituents are prepared, and these are studied spectroscopically, structurally, and computationally. The yellow-orange color of the complexes is additionally explained through time-dependent density functional theory calculations.

Uncatalyzed Hydrogenation of First-Row Main Group Multiple Bonds.

Room temperature hydrogenation of an SIDep-stabilized diboryne (SIDep=1,3-bis(diethylphenyl)-4,5-dihydroimidazol-2-ylidene) and a cAAC-supported diboracumulene (cAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) provided the first selective route to the corresponding 1,2-dihydrodiborenes. DFT calculations showed an overall exothermic (ΔG=19.4 kcal mol-1 ) two-step asynchronous H2 addition mechanism proceeding via a bridging hydride.

Elucidating the Reactivity of Vicinal Dicarbenoids: From Lewis Adduct Formation to B-C Bond Activation.

The reactivity of the diaminoacetylene Pip-C≡C-Pip (Pip=piperidyl=NC5 H10 ) towards phenyldichloro- and triphenylborane is presented. In the case of the less Lewis acidic PhBCl2 , the first example of a double Lewis adduct of a vicinal dicarbenoid is reported. For the more Lewis acidic triphenylborane, coordination to the bifunctional carbene leads to a mild B-C bond activation, resulting in a syn-1,2-carboboration. Ensuing cis/trans isomerization yields a novel ethylene-bridged frustrated Lewis pair (FLP). The compounds were characterized using multinuclear NMR spectroscopy, structural analysis, and mass spectrometry. Reactivity studies of both isomers with the N-heterocyclic carbene 1,3-dimethylimidazol-2-ylidene (IMe) aided in elucidating the proposed isomerization pathway. DFT calculations were carried out to elucidate the reaction mechanism. The rather low free energy of activation is consistent with the observation that the reaction proceeds smoothly at room temperature.

Interactions of Isonitriles with Metal-Boron Bonds: Insertions, Coupling, Ring Formation, and Liberation of Monovalent Boron.

Boryl, borylene, and base-stabilized borylene complexes of manganese and iron undergo a range of different reactions when treated with isonitriles including single, double, and partial isonitrile insertions into metal-boron bonds, ring formation, isonitrile coupling, and the liberation of new monovalent boron species. Two of the resulting cyclic species have also been found to react selectively with anhydrous HCl to form ring-opened products. The diverse isonitrile-promoted reactivity of transition-metal-boron compounds has been explored computationally.

Mild and Complete Carbonyl Ligand Scission on a Mononuclear Transition Metal Complex.

The complete scission of the carbon-oxygen bond of carbon monoxide, while frequently observed on bulk metals and with bimetallic and cluster transition metal complexes, is unknown with monometallic systems. Reaction of a zerovalent iron bis(borylene) complex with a cyclic (alkyl)(amino)carbene revealed a highly selective intramolecular cleavage of the C-O bond of a carbonyl ligand at room temperature, leading to the formation of a highly unusual iron complex containing a base-stabilized (bora)alkylideneborane ligand. DFT investigation of the reaction mechanism suggested that the two Lewis acidic borylene boron atoms cooperate to cleave the C-O multiple bond.

Neutral Diboron Analogues of Archetypal Aromatic Species by Spontaneous Cycloaddition.

Among the numerous routes organic chemists have developed to synthesize benzene derivatives and heteroaromatic compounds, transition-metal-catalyzed cycloaddition reactions are the most elegant. In contrast, cycloaddition reactions of heavier alkene and alkyne analogues, though limited in scope, proceed uncatalyzed. In this work we present the first spontaneous cycloaddition reactions of lighter alkene and alkyne analogues. Selective addition of unactivated alkynes to boron-boron multiple bonds under ambient conditions yielded diborocarbon equivalents of simple aromatic hydrocarbons, including the first neutral 6 π-aromatic diborabenzene compound, a 2 π-aromatic triplet biradical 1,3-diborete, and a phosphine-stabilized 2 π-homoaromatic 1,3-dihydro-1,3-diborete. DFT calculations suggest that all three compounds are aromatic and show frontier molecular orbitals matching those of the related aromatic hydrocarbons, C6 H6 and C4 H4 (2+) , and homoaromatic C4 H5 (+) .

Generation of Dicoordinate Boron(I) Units by Fragmentation of a Tetra-Boron(I) Molecular Square.

Reduction of carbene-borane adduct [(cAAC)BBr2 (CN)] (cAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) cleanly yielded the tetra(cyanoborylene) species [(cAAC)B(CN)]4 presenting a 12-membered (BCN)4 ring. The analysis of the Kohn-Sham molecular orbitals showed significant borylene character of the BI atoms. [(cAAC)B(CN)]4 was found to reduce two equivalents of AgCN per boron center to yield [(cAAC)B(CN)3 ] and fragmented into two-coordinate boron(I) units upon reaction with IMeMe (1,3,4,5-tetramethylimidazol-2-ylidene) to yield the corresponding tricoordinate mixed cAAC-NHC cyanoborylene. The analogous cAAC-phosphine cyanoborylene was obtained by reduction of [(cAAC)BBr2 (CN)] in the presence of excess phosphine.

f-Block Ansa Complexes in the Solid State: [3]Thoro- and [3]Uranocenophanes.

The preparation of [3]thoro- and [3]uranocenophanes, the first structurally authenticated ansa-bridged complexes of actinocenes, is reported. Following a flytrap route, 1,2-bis(cyclooctatetraenyldimethylsilyl)methane was synthesized, reduced to its tetraanion, and subsequently converted into bridged uranocene and thorocene complexes by salt metathesis with the corresponding actinide tetrachlorides. In addition, their electronic structures have been investigated by experimental (UV/Vis spectroscopy, cyclic voltammetry) and theoretical (DFT) methods.

Ansa-bridged bis(benzene) titanium complexes.

Taking advantage of an improved synthesis of [Ti(η(6) -C6 H6 )2 ], we report here the first examples of ansa-bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η(6) -C6 H6 )2 ] with nBuLi in the presence of N,N,N',N'',N''-pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1'-dilithio salt [Ti(η(6) -C6 H5 Li)2 ]⋅pmdta that enables the preparation of the first one- and two-atom-bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X-ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η(6) -C6 H6 )2 ] is found to react with the Lewis base 1,3-dimethylimidazole-2-ylidene (IMe) to give the bent sandwich complex [Ti(η(6) -C6 H6 )2 (IMe)].

Correlations and Contrasts in Homo- and Heteroleptic Cyclic (Alkyl)(amino)carbene-Containing Pt(0) Complexes.

An improved synthetic route to homoleptic complex [Pt(CAAC(Me))2] (CAAC = cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAAC(Me))(PR3)] are presented. Although the homoleptic complex was found to be inert to many reagents, oxidative addition and metal-only Lewis pair (MOLP) formation was observed from one of the heteroleptic complexes. The spectroscopic, structural, and electrochemical properties of the zero-valent complexes were explored in concert with density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The homoleptic [Pt(CAAC)2] and heteroleptic [Pt(CAAC)(PR3)] complexes were found to be similar in their spectroscopic and structural properties, but their electrochemical behavior and reactivity differ greatly. The unusually strong color of the CAAC-containing Pt(0) complexes was investigated by TD-DFT calculations and attributed to excitations into the LUMOs of the complexes, which are predominantly composed of bonding π interactions between Pt and the CAAC carbon atoms.

Formation of BN Isosteres of Azo Dyes by Ring Expansion of Boroles with Azides.

Herein, we present the results of our investigations on the effect of ortho substitution of aryl azides on the ring-expansion reaction of boroles, five-membered unsaturated boron heterocycles. These studies led to the isolation of the first 1,2-azaborinine-substituted azo dyes, which are bright yellow solids. One of the derivatives, (E)-2-mesityl-1-(mesityldiazenyl)-3,4,5,6-tetraphenyl-1,2-azaborinine, was found to be unstable in solution and to transform through a Jacobsen-like reaction into an indazole and 1-hydro-1,2-azaborinine. DFT calculations were performed to shed light on possible mechanisms to rationalize the unexpected azo-azaborinine formation and to draw conclusions about the role played by the ortho substituents in the reaction.

Cyclization of a 1,4-diborabutadiene ligand with both atoms of CO.

A 1,4-dibora-1,3-butadiene iron complex was successfully synthesized through the stoichiometric reaction of an iron bis(borylene) complex with diphenylacetylene. This complex was treated with CO and PMe3 , which led to the formation of an unusual six-membered B2 C3 O ylidic ring bound to both the PMe3 group and zerovalent iron center. The reaction is a very rare example of the incorporation of both atoms of CO into a ring system.

End-on and side-on π-acid ligand adducts of gold(I): carbonyl, cyanide, isocyanide, and cyclooctyne gold(I) complexes supported by N-heterocyclic carbenes and phosphines.

N-heterocyclic carbene ligand SIDipp (SIDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) and trimesitylphosphine ligand have been used in the synthesis of gold(I) cyanide, t-butylisocyanide, and cyclooctyne complexes (SIDipp)Au(CN) (3), (Mes(3)P)Au(CN) (4), [(Mes(3)P)(2)Au][Au(CN)(2)] (5), [(SIDipp)Au(CN(t)Bu)][SbF(6)] ([6][SbF(6)]), [(SIDipp)Au(cyclooctyne)][SbF(6)] ([8][SbF(6)]), and [(Mes(3)P)Au(cyclooctyne)][SbF(6)] ([9][SbF(6)]). A detailed computational study has been carried out on these and the related gold(I) carbonyl adducts [(SIDipp)Au(CO)][SbF(6)] ([1][SbF(6)]), [(Mes(3)P)Au(CO)][SbF(6)] ([2][SbF(6)]), and [(Mes(3)P)Au(CN(t)Bu)](+) ([7](+)). X-ray crystal structures of 3, 5, [6][SbF(6)], [8][SbF(6)], and [9][SbF(6)] revealed that they feature linear gold sites. Experimental and computational data show that the changes in π-acid ligand on (SIDipp)Au(+) from CO, CN(-), CN(t)Bu, cyclooctyne as in [1](+), 3, [6](+), and [8](+) did not lead to large changes in the Au-C(carbene) bond distances. A similar phenomenon was also observed in Au-P distance in complexes [2](+), 4, [7](+), and [9](+) bearing trimesitylphosphine. Computational data show that the Au-L bonds of "naked" [Au-L](+) or SIDipp and Mes(3)P supported [Au-L](+) (L = CO, CN(-), CN(t)Bu to cyclooctyne) have higher electrostatic character than covalent character. The Au←L σ-donation and Au→L π-back-donation contribute to the orbital term with the former being the dominant component, but the latter is not negligible. In the Au-CO adducts [1](+)and [2](+), the cationic gold center causes the polarization of the C-O σ and π orbitals toward the carbon end making the coefficients at the two atoms more equal which is mainly responsible for the large blue shift in the CO stretching frequency. The SIDipp and Mes(3)P supported gold(I) complexes of cyanide and isocyanide also exhibit a significant blue shift in υ(CN) compared to that of the free ligands. Calculated results for Au(CO)Cl and Au(CF(3))CO suggest that the experimentally observed blue shift in ν(CO) of these compounds may at least partly be caused by intermolecular forces.

Borylene complexes (BH)L2 and nitrogen cation complexes (N+)L2: isoelectronic homologues of carbones CL2.

Quantum chemical calculations using DFT (BP86, M05-2X) and ab initio methods (CCSD(T), SCS-MP2) have been carried out on the borylene complexes (BH)L(2) and nitrogen cation complexes (N(+))L(2) with the ligands L=CO, N(2), PPh(3), NHC(Me), CAAC, and CAAC(model). The results are compared with those obtained for the isoelectronic carbones CL(2). The geometries and bond dissociation energies of the ligands, the proton affinities, and adducts with the Lewis acids BH(3) and AuCl were calculated. The nature of the bonding has been analyzed with charge and energy partitioning methods. The calculated borylene complexes (BH)L(2) have trigonal planar coordinated boron atoms which possess rather short B-L bonds. The calculated bond dissociation energies (BDEs) of the ligands for complexes where L is a carbene (NHC or CAAC) are very large (D(e) =141.6-177.3 kcal mol(-1)) which suggest that such species might become isolated in a condensed phase. The borylene complexes (BH)(PPh(3))(2) and (BH)(CO)(2) have intermediate bond strengths (D(e) =90.1 and 92.6 kcal mol(-1)). Substituted homologues with bulky groups at boron which protect the boron atom from electrophilic attack might also be stable enough to become isolated. The BDE of (BH)(N(2))(2) is much smaller (D(e) =31.9 kcal mol(-1)), but could become observable in a low-temperature matrix. The proton affinities of the borylene complexes are very large, particularly for the bulky adducts with L=PPh(3), NHC(Me), CAAC(model) and CAAC and thus, they are superbases. All (BH)L(2) molecules bind strongly AuCl either η(1) (L=N(2), PPh(3), NHC(Me), CAAC) or η(2) (L=CO, CAAC(model)). The BDEs of H(3)B-(BH)L(2) adducts which possess a hitherto unknown boron→boron donor-acceptor bond are smaller than for the AuCl complexes. The strongest bonded BH(3) adduct that might be isolable is (BH)(PPh(3))(2)-BH(3) (D(e) =36.2 kcal mol(-1)). The analysis of the bonding situation reveals that (BH)-L(2) bonding comes mainly from the orbital interactions which has three major contributions, that is, the donation from the symmetric (σ) and antisymmetric (π(||)) combination of the ligand lone-pair orbitals into the vacant MOs of BH L→(BH)←L and the L←(BH)→L π backdonation from the boron lone-pair orbital. The nitrogen cation complexes (N(+))L(2) have strongly bent L-N-L geometries, in which the calculated bending angle varies between 113.9° (L=N(2)) and 146.9° (L=CAAC). The BDEs for (N(+))L(2) are much larger than those of the borylene complexes. The carbene ligands NHC and CAAC but also the phosphane ligands PPh(3) bind very strongly between D(e) =358.4 kcal mol(-1) (L=PPh(3)) and D(e) =412.5 kcal mol(-1) (L=CAAC(model)). The proton affinities (PA) of (N(+))L(2) are much smaller and they bind AuCl and BH(3) less strongly compared with (BH)L(2). However, the PAs (N(+))L(2) for complexes with bulky ligands L are still between 139.9 kcal mol(-1) (L=CAAC(model)) and 168.5 kcal mol(-1) (L=CAAC). The analysis of the (N(+))-L(2) bonding situation reveals that the binding interactions come mainly from the L→(N(+))←L donation while L←(N(+) )→L π backdonation is rather weak.

Isolable tris(alkyne) and bis(alkyne) complexes of gold(I).

Golden trefoils: Tris(alkyne)gold complex [(coct)(3)Au][SbF(6)] (see picture; 1-SbF(6)) can be synthesized from cyclooctyne (coct) and AuSbF(6) generated in situ. Treatment of AuCl with cyclooctyne led to the bis(alkyne)gold complex [Au(coct)(2)Cl] (2). DFT analysis indicates that the cyclooctyne ligands are net electron donors in 1 but overall electron acceptors in 2. AuSbF(6) is shown to mediate [2+2+2] cycloaddition reactions of alkynes.