Comparing the Electronic Structure of Iron, Cobalt, and Nickel Compounds That Feature a Phosphine-Substituted Bis(imino)pyridine Chelate.

It was recently discovered that (Ph2PPrPDI)Mn (PDI = pyridine diimine) exists as a superposition of low-spin Mn(II) that is supported by a PDI dianion and intermediate-spin Mn(II) that is antiferromagnetically coupled to a triplet PDI dianion, a finding that encouraged the synthesis and electronic structure evaluation of late first row metal variants that feature the same chelate. The addition of Ph2PPrPDI to FeBr2 resulted in bromide dissociation and the formation of [(Ph2PPrPDI)FeBr][Br]. Reduction of this precursor using excess sodium amalgam afforded (Ph2PPrPDI)Fe, which possesses an Fe(II) center that is supported by a dianionic PDI ligand. Similarly, reduction of a premixed solution of Ph2PPrPDI and CoCl2 yielded the cobalt analog, (Ph2PPrPDI)Co. EPR spectroscopy and density functional theory calculations revealed that this compound features a high-spin Co(I) center that is antiferromagnetically coupled to a PDI radical anion. The addition of Ph2PPrPDI to Ni(COD)2 resulted in ligand displacement and the formation of (Ph2PPrPDI)Ni, which was found to possess a pendent phosphine group. Single-crystal X-ray diffraction, CASSCF calculations, and EPR spectroscopy indicate that (Ph2PPrPDI)Ni is best described as having a Ni(II)-PDI2- configuration. The electronic differences between these compounds are highlighted, and a computational analysis of Ph2PPrPDI denticity has revealed the thermodynamic penalties associated with phosphine dissociation from 5-coordinate (Ph2PPrPDI)Mn, (Ph2PPrPDI)Fe, and (Ph2PPrPDI)Co.

Reaction of a Molybdenum Bis(dinitrogen) Complex with Carbon Dioxide: A Combined Experimental and Computational Investigation.

Refluxing Mo(CO)6 in the presence of the phosphine-functionalized α-diimine ligand Ph2PPrDI allowed for substitution and formation of the dicarbonyl complex, (Ph2PPrDI)Mo(CO)2. Oxidation with I2 followed by heating resulted in further CO dissociation and isolation of the corresponding diiodide complex, (Ph2PPrDI)MoI2. Reduction of this complex under a N2 atmosphere afforded the corresponding bis(dinitrogen) complex, (Ph2PPrDI)Mo(N2)2. The solid-state structures of all three compounds were found to feature a tetradentate chelate and cis-monodentate ligands. Notably, the addition of CO2 to (Ph2PPrDI)Mo(N2)2 is proposed to result in head-to-tail CO2 coupling to generate the corresponding metallacycle and ultimately a mixture of (Ph2PPrDI)Mo(CO)2 and the bis(oxo) dimer, [(κ3-Ph2PPrDI)Mo(O)(µ-O)]2. Computational studies have been performed to gain insight into the reaction and evaluate the importance of cis-coordination sites for selective head-to-tail CO2 reductive coupling, CO deinsertion, disproportionation, and stepwise CO2 deinsertion.

Respiratory failure in a 28-year-old male.

An interesting case of respiratory failure secondary to occupational exposure in a 28-year-old male http://bit.ly/2SzR6dK.

Efficient Cobalt Catalyst for Ambient-Temperature Nitrile Dihydroboration, the Elucidation of a Chelate-Assisted Borylation Mechanism, and a New Synthetic Route to Amides.

N,N-Diborylamines have emerged as promising reagents in organic synthesis; however, their efficient preparation and full synthetic utility have yet to be realized. To address both shortcomings, an effective catalyst for nitrile dihydroboration was sought. Heating CoCl2 in the presence of PyEtPDI afforded the six-coordinate Co(II) salt, [(PyEtPDI)CoCl][Cl]. Upon adding 2 equiv of NaEt3BH, hydride transfer to one chelate imine functionality was observed, resulting in the formation of (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Single-crystal X-ray diffraction and density functional theory calculations revealed that this compound possesses a low-spin Co(II) ground state featuring antiferromagnetic coupling to a singly reduced imino(pyridine) moiety. Importantly, (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co was found to catalyze the dihydroboration of nitriles using HBPin with turnover frequencies of up to 380 h-1 at ambient temperature. Stoichiometric addition experiments revealed that HBPin adds across the Co-Namide bond to generate a hydride intermediate that can react with additional HBPin or nitriles. Computational evaluation of the reaction coordinate revealed that the B-H addition and nitrile insertion steps occur on the antiferromagnetically coupled triplet spin manifold. Interestingly, formation of the borylimine intermediate was found to occur following BPin transfer from the borylated chelate arm to regenerate (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Borylimine reduction is in turn facile and follows the same ligand-assisted borylation pathway. The independent hydroboration of alkyl and aryl imines was also demonstrated at 25 °C. With a series of N,N-diborylamines in hand, their addition to carboxylic acids allowed for the direct synthesis of amides at 120 °C, without the need for an exogenous coupling reagent.

Atypia of Undetermined Significance in Thyroid Fine-Needle Aspirations: Follow-Up and Outcome Experience in Newfoundland, Canada.

INTRODUCTION: The rates of atypia of undetermined significance (AUS) by fine-needle aspiration (FNA) and malignant outcomes have been estimated at < 7% and 5-15%, respectively. Initial AUS diagnosis is followed up clinically with serial ultrasounds, repeat FNA, molecular testing, or direct surgery. We investigated the incidence, follow-up modalities, and final outcomes of AUS in Newfoundland. METHODS: All cases of AUS diagnosed at the Eastern Health Cytology Laboratory between 1 January 2010 and 31 December 2013 were identified. Electronic medical records were examined for follow-up modalities and final histologic diagnosis. The final outcomes were reported as benign, malignant, or undetermined. RESULTS: Out of 3,285 thyroid FNAs, 181 (5.5%) were AUS. Fifty-seven (31.5%) had repeat FNA diagnosed as benign (38.6%), AUS (29.8%), or suspicious/malignant (8.8%). Eighty-four (46.4%) had surgery after the first AUS diagnosis, 39 (46.4%) of which were malignant. Twenty-four patients (13.3%) were followed up by serial ultrasound only, 2 (1.1%) by molecular testing, and 1 (0.6%) died of unrelated disease. Thirteen (7.2%) had no follow-up record. Our malignancy rate (MR) was 29.8%. CONCLUSION: The MR in our population was higher than the rate proposed by The Bethesda System for Reporting Thyroid Cytopathology. Repeat FNA can reduce the rate of unnecessary surgeries, but practice guidelines should consider individual and institutional circumstances. The ratio MR:ADR (AUS diagnostic rate) may be a better indicator of performance.

Two-step C-H, C-P bond activation at an α-diimine iron dinitrogen complex.

Reduction of 6-coordinate ((Ph2PPr)DI)FeBr2 under N2 results in formation of the terminal dinitrogen complex, ((Ph2PPr)DI)FeN2. Heating this product to 75 °C allows for C-H and C-P activation of the chelate to generate the cisoid and transoid isomers of [(µ-PrPPh-κ(5)-P,N,N,Cγ,P-(Ph2PPr)DI(PrPPh))Fe]2. Mechanistic possibilities for this transformation are discussed.

A Pentacoordinate Mn(II) Precatalyst That Exhibits Notable Aldehyde and Ketone Hydrosilylation Turnover Frequencies.

Heating (THF)2MnCl2 in the presence of the pyridine-substituted bis(imino)pyridine ligand, (PyEt)PDI, allowed preparation of the respective dihalide complex, ((PyEt)PDI)MnCl2. Reduction of this precursor using excess Na/Hg resulted in deprotonation of the chelate methyl groups to yield the bis(enamide)tris(pyridine)-supported product, (κ(5)-N,N,N,N,N-(PyEt)PDEA)Mn. This complex was characterized by single-crystal X-ray diffraction and found to possess an intermediate-spin (S = (3)/2) Mn(II) center by the Evans method and electron paramagnetic resonance spectroscopy. Furthermore, (κ(5)-N,N,N,N,N-(PyEt)PDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min(-1) when employed under solvent-free conditions. This optimization allowed for isolation of the respective alcohols and, in two cases, the partially reacted silyl ethers, PhSiH(OR)2 [R = Cy and CH(Me)((n)Bu)]. The aldehyde hydrosilylation activity observed for (κ(5)-N,N,N,N,N-(PyEt)PDEA)Mn renders it one of the most efficient first-row transition metal catalysts for this transformation reported to date.

Estrogen and progesterone receptors expression in gastrointestinal stromal tumors and intramural gastrointestinal leiomyomas.

Gastrointestinal stromal tumors (GISTs) and leiomyomas of the gastrointestinal tract both may present as intramural smooth muscle cell tumors. Immunohistochemically, these tumors demonstrate different spectrums of protein expression, which helps in differential diagnosis. Leiomyomas of the uterine type are similar by the spectrum of protein expression to gastrointestinal leiomyomas, but they express in addition both estrogen (ER) and progesterone (PR) receptors, which makes hormonal therapy possible for these tumors. In the current study, we investigated expression of ER and PR in GISTs and intramural gastrointestinal leiomyomas. Our data demonstrate that none of the 22 cases of gastrointestinal leiomyomas nor 19 cases of GIST were positive for either ER or PR expression. In contrast, leiomyomas of the uterine type were strongly positive for both ER and PR. Our data demonstrate that GIST and gastrointestinal leiomyomas differ from leiomyomas of the uterine type by the expression of ER and PR. Immunostaining for ER and PR may be a useful tool to distinguish these tumors and more precisely to plan further clinical interventions.