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ChemInform Abstract The sequential reactions of the acyl complexes (I) shown in the scheme give crystalline vinylidene complexes as mixture of the geometric isomers (II) and (III). The thermodynamic synclinal isomers (II) are favored at room temperature. In CD2Cl2 these geometric isomers equilibrate. Photolysis gives (50:50) photostationary states. An X-ray structure analysis of the PF6 salt of the synclinal complex cation (IId) (space group C2/c, Z = 8) confirms the naphthyl substituent to be anti to the bulky PPh3 ligand. Reactions of (II)/(III) with base yield the acetylide complexes (IV). These react with TFA at -78 rc C (assayed by NMR) to give 98:2, > 99:1, and > 99:1 mixtures of (IIIb)/(IIb), (IIIc)/(IIc), and (IIId)/(IId). Kinetic and activation parameters for the thermal isomerization of (III) to (II) are determined. Analogous Cβ methylation reactions of (IV) are similarly stereospecific; (IVb) gives (VI). The structure of (IVb) (P1-, Z=2) is established by X-ray analysis. Reactions of (IIb), (IIIb), and its dimethyl analogue (VI) with PMe3 (IX) produce the α-phosphoniovinyl complexes (VII) indicating preferential attack on the Cα face opposite to PPh3.

The complex (7?5-C5H5XCO)2FeC^CC^CH was prepared by sequential treatment of LiC=CC^=C-SHCH3)3 with (775-C5H5XCO)2FeCI and tetrabutylammonium fluoride. The monometallic complexes (?75-C5H5)(CO)-LFeC=CC=CH (L = CO, PPh3) were deprotonated with sec-BuLi, and the resulting anions were trapped with (j75-C5H5)M(CO)"CI to form (7?5-C5H5XCO)LFeC=cC=CM-(CO)"foe-

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Objective. Most brain–computer interfaces (BCIs) based on functional near-infrared spectroscopy (fNIRS) require that users perform mental tasks such as motor imagery, mental arithmetic, or music imagery to convey a message or to answer simple yes or no questions. These cognitive tasks usually have no direct association with the communicative intent, which makes them difficult for users to perform. Approach. In this paper, a 3-class intuitive BCI is presented which enables users to directly answer yes or no questions by covertly rehearsing the word ‘yes’ or ‘no’ for 15 s. The BCI also admits an equivalent duration of unconstrained rest which constitutes the third discernable task. Twelve participants each completed one offline block and six online blocks over the course of two sessions. The mean value of the change in oxygenated hemoglobin concentration during a trial was calculated for each channel and used to train a regularized linear discriminant analysis (RLDA) classifier. Main results. By the final online block, nine out of 12 participants were performing above chance (p  <  0.001 using the binomial cumulative distribution), with a 3-class accuracy of 83.8%  ±  9.4%. Even when considering all participants, the average online 3-class accuracy over the last three blocks was 64.1 %  ±  20.6%, with only three participants scoring below chance (p  <  0.001). For most participants, channels in the left temporal and temporoparietal cortex provided the most discriminative information. Significance. To our knowledge, this is the first report of an online 3-class imagined speech BCI. Our findings suggest that imagined speech can be used as a reliable activation task for selected users for development of more intuitive BCIs for communication.