The hydroamination of heterocumulenes such as carbodiimides, isocyanates, and isothiocyanates by a bis(phosphinoselenoic amide) supported titanium(iv) complex as a precatalyst is reported here. The ...titanium(iv) complex {Ph
P(Se)NCH
CH
NPPh
(Se)}Ti(NMe
)
(1) was synthesised by the reaction of tetrakis-(dimethylamido)titanium(iv) Ti(NMe
)
with {Ph
P(Se)NHCH
CH
NHPPh
(Se)} in toluene at ambient temperature. Titanium complex 1 proved to be a competent pre-catalyst for the addition of an amine N-H bond to carbodiimides, isocyanates, and isothiocyanates. The reaction scope was expanded to reactions of aliphatic and aromatic amines with phenylisocyanates and phenylisothiocyanates in toluene solvents proceeding rapidly at room temperature with 5 mol% catalyst loadings to yield the corresponding urea and thio-urea derivatives up to 99%. However, ambient temperature was needed for hydroamination of 1,3-dicyclohexylcarbodiimide. The amine addition reactions with isocyanates showed first order kinetics with respect to catalyst 1 as well as substrates. The most plausible mechanism for the hydroamination reaction was established by isolating 1,1-dimethylphenyl urea as a side product.
Literature is highly inconsistent in describing the proximal attachment of the anterolateral ligament (ALL) and its relationship with the lateral collateral ligament (LCL) in human knees. This ...observational study aims to investigate that lacuna. The gross dissection was performed in the lower limbs (n = 83) from the donated adult-age (> 18 years) embalmed cadavers from medical institutions in the north and east India. The dissected knee specimens were first examined macroscopically. Further routine and special staining and microscopic examinations were performed. The ALL was absent in approximately 20.4% of the studied knee specimens (17/83). In remaining, the sharing of ALL and LCL proximal fibers was observed as a consistent finding (~ 97%) with rare exceptions. The mean length of the tibial and meniscal limbs of ALL was 1.57 ± 0.8 cm Range (R) 0.5-4 cm and 0.73 ± 0.47 cm Range (R) 0.1-1.6 cm, respectively. In addition, multiple variations in its presentation were observed. We propose that the proximal sharing of LCL-ALL fibers is a dominant feature in the studied population. The sharing of the fibers may impact the biomechanics and injury mechanisms for both ligaments. The possibility of ethnic variations in the ALL morphology should be a concern during reconstruction surgery.
Randomised trial data assessing the safety and efficacy of the self-expanding intra-annular Portico transcatheter aortic valve system (Abbott Structural Heart, St Paul, MN, USA) compared with any ...commercially available valves are needed to compare performance among designs.
In this prospective, multicentre, non-inferiority, randomised controlled trial (the Portico Re-sheathable Transcatheter Aortic Valve System US Investigational Device Exemption trial PORTICO IDE), high and extreme risk patients with severe symptomatic aortic stenosis were recruited from 52 medical centres experienced in performing transcatheter aortic valve replacement in the USA and Australia. Patients were eligible if they were aged 21 years or older, in New York Heart Association functional class II or higher, and had severe native aortic stenosis. Eligible patients were randomly assigned (1:1) using permuted block randomisation (block sizes of 2 and 4) and stratified by clinical investigational site, surgical risk cohort, and vascular access method, to transcatheter aortic valve replacement with the first generation Portico valve and delivery system or a commercially available valve (either an intra-annular balloon-expandable Edwards-SAPIEN, SAPIEN XT, or SAPIEN 3 valve Edwards LifeSciences, Irvine, CA, USA; or a supra-annular self-expanding CoreValve, Evolut-R, or Evolut-PRO valve Medtronic, Minneapolis, MN, USA). Investigational site staff, implanting physician, and study participant were unmasked to treatment assignment. Core laboratories and clinical event assessors were masked to treatment allocation. The primary safety endpoint was a composite of all-cause mortality, disabling stroke, life-threatening bleeding requiring transfusion, acute kidney injury requiring dialysis, or major vascular complication at 30 days. The primary efficacy endpoint was all-cause mortality or disabling stroke at 1 year. Clinical outcomes and valve performance were assessed up to 2 years after the procedure. Primary analyses were by intention to treat and the Kaplan-Meier method to estimate event rates. The non-inferiority margin was 8·5% for primary safety and 8·0% for primary efficacy endpoints. This study is registered with ClinicalTrials.gov, NCT02000115, and is ongoing.
Between May 30 and Sept 12, 2014, and between Aug 21, 2015, and Oct 10, 2017, with recruitment paused for 11 months by the funder, we recruited 1034 patients, of whom 750 were eligible and randomly assigned to the Portico valve group (n=381) or commercially available valve group (n=369). Mean age was 83 years (SD 7) and 395 (52·7%) patients were female. For the primary safety endpoint at 30 days, the event rate was higher in the Portico valve group than in the commercial valve group (52 13·8% vs 35 9·6%; absolute difference 4·2, 95% CI −0·4 to 8·8 upper confidence bound {UCB} 8·1%; pnon-inferiority=0·034, psuperiority=0·071). At 1 year, the rates of the primary efficacy endpoint were similar between the groups (55 14·8% in the Portico group vs 48 13·4% in the commercial valve group; difference 1·5%, 95% CI −3·6 to 6·5 UCB 5·7%; pnon-inferiority=0·0058, psuperiority=0·50). At 2 years, rates of death (80 22·3% vs 70 20·2%; p=0·40) or disabling stroke (10 3·1% vs 16 5·0%; p=0·23) were similar between groups.
The Portico valve was associated with similar rates of death or disabling stroke at 2 years compared with commercial valves, but was associated with higher rates of the primary composite safety endpoint including death at 30 days. The first-generation Portico valve and delivery system did not offer advantages over other commercially available valves.
Abbott.
We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand 2-(Ph3CN=CH)C4H3NH (1-H) moiety in their coordination sphere, synthesized using either ...alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition Li(2-(Ph3CN=CH)C4H3N)(THF)2 (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition (2-(Ph3CN=CH)C4H3N)Na(THF)2 (3) and (2-(Ph3CN=CH)C4H3N)K(THF)0.54 (4) respectively. The magnesium complex of composition (THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N} (5) was synthesized through the alkane elimination method, in which Mg(CH2Ph)2(OEt2)2 was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex (THF)2Mg{2-(Ph3CN=CH)C4H3N}2 (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3 were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor M{N(SiMe3)2}2(THF)n (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very narrow polydispersity index in comparison to that of magnesium complexes 5 and 6.
We report here a series of heavier alkaline earth metal complexes with a phosphinoselenoic amide ligand using two synthetic routes. In the first route, the heavier alkaline earth metal ...bis(trimethylsilyl)amides M{N(SiMe3)2}2(THF)n (M = Ca, Sr, Ba) were treated with phosphinoselenoic amine Ph2P(Se)NH(CHPh2) (3), prepared by the treatment of bulky phosphinamines Ph2PNH(CHPh2) (1) with elemental selenium in THF, and afforded homoleptic alkaline earth metal complexes of composition M(THF)2{Ph2P(Se)N(CHPh2)}2 (M = Ca (7), Sr (8), Ba (9)). The metal complexes 7–9 can also be obtained via salt metathesis route where the alkali metal phosphinoselenoic amides of composition {(THF)2M′Ph2P(Se)N(CHPh2)}2 (M′ = Na (5) and K (6)) were reacted with respective metal diiodides in THF at ambient temperature. The solid state structures of the alkali metal complexes 5–6 and alkaline earth metal complexes 7–9 were established by single crystal X-ray diffraction analysis. In the solid state, alkali metal complexes 5 and 6 are dimeric and form a poly-metallacyclic structural motif. In contrast, complexes 7–9 are monomeric and a direct metal–selenium bond is observed in each case.
We report here a series of enantiomeric pure alkaline earth metal complexes, each with a metallic direct bond of selenium, with {HN(
R
-*CHMePh)(P(Se)Ph
2
)} (
1a
) and {HN(
S
-*CHMePh)(P(Se)Ph
2
)} ...(
1b
), synthesised using two routes. The first route involves a trans metalation reaction of enantiomeric pure potassium phosphinoselenoic amide K{N(
R
-*CHMePh)(Ph
2
P(Se))}{THF}
n
(
2a
) or K{N(
S
-*CHMePh)(Ph
2
P(Se))}{THF}
n
(
2b
) prepared from the reaction between either
1a
or
1b
and KN(SiMe
3
)
2
, and the corresponding alkaline earth metal diiodies in THF at room temperature to afford the enantiomeric pure complexes of composition M{N(
R
-*CHMePh)P(Se)Ph
2
}
2
(THF)
n
M = Mg (
3a
),
n
= 1; M = Ca (
4a
), Sr (
5a
) and Ba (
6a
),
n
= 2 and M{N(
S
-*CHMePh)P(Se)Ph
2
}
2
(THF)
n
M = Mg (
3b
),
n
= 1; M = Ca (
4b
), Sr (
5b
) and Ba (
6b
),
n
= 2. The same heavier alkaline earth metal complexes (
4a–6a
and
4b–6b
) can also be obtained through the silylamine elimination method using the corresponding metal bis(trimethylsilyl)amides M{N(SiMe
3
)
2
}
2
(THF)
n
(M = Ca, Sr, Ba) with phosphinoselenoic amine ligands
1a
and
1b
in ambient conditions. The solid-state structures of the metal complexes
4a–6a
and
4b–6b
were established using single-crystal X-ray diffraction analysis. In the solid state, all the metal complexes crystallise in the monoclinic
P
2
1
space group and each phosphinoselenoic amido ligand is ligated to the metal ion in a bidentate fashion. We also report the syntheses and structures of chiral amidophosphine-borane ligands {HN(
R
-*CHMePh)(P(BH
3
)Ph
2
)} (
7a
) and {HN(
S
-*CHMePh)(P(BH
3
)Ph
2
)} (
7b
) and the corresponding homoleptic barium complexes of composition Ba{N(
R
-*CHMePh)P(BH
3
)Ph
2
}
2
(THF)
2
(
8a
) and Ba{N(
R
-*CHMePh)P(BH
3
)Ph
2
}
2
(THF)
2
(
8b
). The molecular structures of
8a
and
8b
in the solid state confirm the attachment of chiral amidophosphine-borane ligands to the barium ions. The complexes
5
and
6
were tested as catalysts for the ring-opening polymerisation of ε-caprolactone. High activity in relation to the barium complexes
6a
and
6b
is observed, with moderate to narrow polydispersity index.
The aim of this study was to characterize the safety profile of an intra-annular self-expanding valve with a next-generation low-profile delivery system (DS).
Key design modifications to the FlexNav ...DS include the addition of a hydrophilic-coated, integrated sheath and stability layer to facilitate gradual, controlled deployment in vessels with diameter ≥5 mm.
Patients were pooled from 2 concurrent prospective, multicenter, single-arm studies (FlexNav DS arm of PORTICO IDE Portico Re-Sheathable Transcatheter Aortic Valve System U.S. IDE Trial n = 134 and the FlexNav EU CE Mark Study n = 46) for the analysis. The primary endpoint was Valve Academic Research Consortium-2–defined major vascular complications at 30 days. Clinical outcomes and valve performance were assessed through 30 days by an independent clinical events committee and an echocardiography core laboratory, respectively.
One hundred forty high-risk and 40 extreme-risk subjects enrolled between October 15, 2018, and December 10, 2019, from 28 sites in the United States, Australia, and Europe who underwent attempted transfemoral Portico valve implantation were included. The mean age was 85.1 ± 5.6 years, 60% were women, the mean Society of Thoracic Surgeons score was 5.3%, and 96.1% presented with ≥1 frailty factor. Technical device success was 96.7%. At 30 days, the rate of major vascular complications was 5.0%, with 4.4% of complications adjudicated as access site-related (3.3% transcatheter aortic valve replacement DS access site-related). Death (0.6%) and disabling stroke (1.1%) were rare. The rate of new permanent pacemaker implantation was 15.4%. Echocardiography revealed a mean gradient of 7.1 ± 3.2 mm Hg, mean valve area of 1.77 ± 0.41 cm2, and a 4.1% rate of moderate paravalvular leak at 30 days.
Portico valve implantation with the FlexNav DS was associated with an excellent safety profile at 30 days.
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We report here a series of heavier alkaline earth metal complexes with N,N'-(ethane-1,2-diyl)bis(P,P-diphenylphosphinoselenoic amide) using two synthetic routes. In the first route, the heavier ...alkaline earth metal bis(trimethylsilyl)amides M{N(SiMe3)2}2(THF)n (M = Ca, Sr, Ba), when treated with phosphinoselenoic amine Ph2P(Se)NHCH2CH2NHPPh2(Se) (1), afforded the corresponding alkaline earth metal complexes of the composition (THF)3M{Ph2P(Se)NCH2CH2NPPh2(Se)} M = Ca (2), Sr (3), Ba (4). The metal complexes 2-4 were also obtained from a one-pot reaction, where potassium phosphinoselenoic amide was generated in situ by the reaction of compound 1 and KN(SiMe3)2, followed by the addition of the respective metal diiodides in THF at room temperature. The magnesium complex (THF)3Mg{Ph2P(Se)NCH2CH2NPPh2(Se)} (5) was also prepared. The solid-state structures of alkaline earth metal complexes 2-5 were established by single crystal X-ray diffraction analysis. In the solid state, all the metal complexes are monomeric but in complexes 2-4, ligand 1 is chelated in a tetra-dentate fashion to each metal ion but in complex 5, ligand 1 behaves as a bidentate ligand. Complexes 2-4 were tested as catalysts for the ring-opening polymerisation of ε-caprolactone and a high level of activity for the barium complex 4 was observed, with narrow polydispersity. We also report the synthesis and structure of the bis(amidophosphino borane) ligand Ph2P(BH3)NHCH2CH2NHPPh2(BH3) (6) and the corresponding barium complex (THF)2Ba{Ph2P(BH3)NCH2CH2NPPh2(BH3)}2 (7).
► Various bulky phosphinamines and derivatives have been synthesized. ► Very straight forward synthesis, i.e. easily accessible of the compounds. ► Novel structural motifs in sodium complexes using ...heteroatoms are observed. ► Three hetero atoms (N, P, S or O) are making the poly metallacycles.
The treatment of two bulky phosphinamines Ph2PNH(CHPh2) (1) and Ph2PNH(CPh3) (2) with 30% hydrogen peroxide afforded phosphinicamides Ph2P(O)NH(CHPh2) (3) and Ph2P(O)NHCPh3 (4) in good yield. When the same phosphinamines are reacted with elemental sulfur, corresponding sulfur compounds Ph2P(S)NH(CHPh2) (5) and Ph2P(S)NHCPh3 (6) are obtained. Further reactions of 4–6 with sodium bis(trimethylsilyl)amide in THF solution afforded corresponding sodium salts of molecular formula {(THF)2Na(Ph2P(O)NCPh3)}2 (8), {(THF)2Na(Ph2P(S)NCHPh2)}2 (7) and {(THF)2Na(Ph2P(S)NCPh3)}{(THF)Na(Ph2P(S)NCPh3)} (9) and all the sodium complexes 7–9 are dimeric and form highly strained polymetallacyclic motif in solid state structures. Molecular structure of all the complexes are established by single crystal X-ray diffraction analysis.
•Two bulky 1,4-diaza-1,3-butadiene ligands were synthesized.•Ligand 2 formed homoleptic and ligand 3 formed heteroleptic copper(I) complexes.•Solid state structures of all the ligand s 2-3 and ...copper(I) complexes 3-5 were established.•Complexes 3-5 were tested as catalyst for the coupling reaction of o-iodophenol and phenyl acetylene.
We report the full characterization of two glyoxal-based ligands N,N bis(diphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh2, 1) and more bulky N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (DADPh3, 2) by the condensation reaction of glyoxal and diphenylmethanamine and triphenyl-methanamine respectively. The copper (I) complex of composition Cu(DADPh2)2PF6 (3) having two neutral bidentate N,N bis(diphenyl-methyl)-1,4-diaza-1,3-butadiene ligand was prepared by the reaction of Cu(CH3CN)4PF6 and 1 in 1:2 ratio in dichloromethane. In a similar reaction with N,N bis(triphenylmethyl)-1,4-diaza-1,3-butadiene ligand (2) and Cu(CH3CN)4PF6 in dichloromethane yielded corresponding heteroleptic copper (I) complex Cu(DADPh3)(CH3CN)2PF6 (4). Another copper (I) complex Cu(DADPh2)(PPh3)PF6 (5) can also be obtained by the one pot reaction involving ligand 1, Cu(CH3CN)4PF6 and triphenylphosphine. Solid state structures of all the five compounds were established by single crystal X-ray diffraction analysis. The solid state structures of the copper complexes 3–5 reveal a distorted tetrahedral geometry around the copper (I) centers. The copper complexes 3–5 were tested as catalysts for the coupling reaction of o-iodophenol and phenyl acetylene and it was observed that complex 4 exhibits the highest catalytic activity.
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