Abstract:The reaction of the unsymmetric bisphosphanyl urea ligand P(OC(6)H(3)Bu(t)(2)-2,4)(2)N(Me)C(O)N(Me)PPh(2) with [Pd(cod)Cl(2)] (cod = 1,5-cyclooctadiene) results in the chiral palladacycle (R,S)(A2)-[Pd(kappa(2)-P,P-[P(OC(6)H(3)Bu(t)(2)-2,4)(2)N(Me)C(O)N(Me)PPh(2)]Cl(2)]. The chirality of the title compound is caused by the tilting of the central, six-membered PdP(2)N(2)C ring along one of the two P-N vectors and comprises two chiral planes and one chiral axis.
“…Very recently, English authors have estimated that the incidence of ONJ in the oncological and osteometabolic population is approximately 10 cases/million/year (Rogers et al, 2015). A wide-ranging incidence of ONJ from 0% to 27.5% has been reported for individuals exposed to intravenous BP (Kuhl et al, 2012). In patients receiving oral NBPs, ONJ data should be treated with caution (Reid, 2009).…”
OBJECTIVE: Osteonecrosis of the jaw (ONJ) is a potentially severe adverse effect of various medications (bisphosphonates, anti-resorptive, and anti-angiogenic drugs). ONJ pathogenesis is still unclear although some risk factors have been recognized. Of these, rheumatoid arthritis (RA) has been hypothesized as a potential risk factor for developing ONJ. This observational study will describe a multicenter case series of patients affected with RA and ONJ, and it will attempt to evaluate the association between features of ONJ and pharmacological, systemic, and site variables. METHODS: Demographic, pharmacological, and clinical data from 18 RA patients with ONJ were collected and registered from three Italian centers (i.e., Palermo, Verona, and Padua) from 2004 to 2013. RESULTS: Sixteen (88.9%) patients were in therapy for RA: 9 of 18 (50.0%) with systemic steroids, 3 of 18 (16.7%) with methotrexate, and 4 of 18 (22.2%) with both medications. Two patients were not receiving treatment for RA. All patients took NBPs for secondary osteoporosis (average NBP duration of 69 months, range: 20-130): Fifteen (83.3%) patients were treated with single NBPs, while three (16.7%) with different molecules; one patient was also treated with denosumab. Mandible was affected more frequently (66.7%) than maxilla (33.3%); one patient presented multiple ONJ events. CONCLUSIONS: This is the first multicenter case series in the international literature regarding our topic. Focusing on our data, it could be hypothesized that patients with RA may be more susceptible to ONJ than the majority of osteometabolic patients. In our opinion, it could be important to monitor also denosumab or other biological drug side effects.
“…Very recently, English authors have estimated that the incidence of ONJ in the oncological and osteometabolic population is approximately 10 cases/million/year (Rogers et al, 2015). A wide-ranging incidence of ONJ from 0% to 27.5% has been reported for individuals exposed to intravenous BP (Kuhl et al, 2012). In patients receiving oral NBPs, ONJ data should be treated with caution (Reid, 2009).…”
OBJECTIVE: Osteonecrosis of the jaw (ONJ) is a potentially severe adverse effect of various medications (bisphosphonates, anti-resorptive, and anti-angiogenic drugs). ONJ pathogenesis is still unclear although some risk factors have been recognized. Of these, rheumatoid arthritis (RA) has been hypothesized as a potential risk factor for developing ONJ. This observational study will describe a multicenter case series of patients affected with RA and ONJ, and it will attempt to evaluate the association between features of ONJ and pharmacological, systemic, and site variables. METHODS: Demographic, pharmacological, and clinical data from 18 RA patients with ONJ were collected and registered from three Italian centers (i.e., Palermo, Verona, and Padua) from 2004 to 2013. RESULTS: Sixteen (88.9%) patients were in therapy for RA: 9 of 18 (50.0%) with systemic steroids, 3 of 18 (16.7%) with methotrexate, and 4 of 18 (22.2%) with both medications. Two patients were not receiving treatment for RA. All patients took NBPs for secondary osteoporosis (average NBP duration of 69 months, range: 20-130): Fifteen (83.3%) patients were treated with single NBPs, while three (16.7%) with different molecules; one patient was also treated with denosumab. Mandible was affected more frequently (66.7%) than maxilla (33.3%); one patient presented multiple ONJ events. CONCLUSIONS: This is the first multicenter case series in the international literature regarding our topic. Focusing on our data, it could be hypothesized that patients with RA may be more susceptible to ONJ than the majority of osteometabolic patients. In our opinion, it could be important to monitor also denosumab or other biological drug side effects.
“…The previously reported palladium complex 1 , easily accessible from the reaction between P(OC 6 H 3 Bu t 2 -2,4) 2 N(Me)C(O)N(Me)PPh 2 and [PdCl 2 (cod)] (cod = 1,5-cyclooctadiene), folds only along one of the two possible fold vectors. In this complex, the PPh 2 phosphorus atom is located on the fold vector, which is evidently the preferred position for the sterically less encumbered phosphorus group.…”
Section: Resultsmentioning
confidence: 99%
“…The racemate can be described as ( R / S ) A2 . For a description of the planar chiral elements, see ref . 2 Chirality of 1 As Described by the Axial Chiral Element A2 (Dotted Line) …”
Section: Resultsmentioning
confidence: 99%
“…The two Cu−P bonds are very similar but not identical (Cu1−P1 222.80(6) pm and Cu1−P2 224.06(5) pm), lying very much at the low end of the range (221.9−229.5 pm), and the P1−Cu1−P2 angle of 93.189(18)° is significantly smaller than tetrahedral. These metallacycles are folded along the P1−N2 vector, creating one axial and two planar elements of chirality . The phosphorus atom on the fold vector (P1) forms the slightly shorter bond to copper.…”
Section: Resultsmentioning
confidence: 99%
“…With the report of PPh 2 NMeC(O)NMeH, the first monophosphinourea possessing an easy to activate functional group, a new field was opened up . This led to the discovery of a facile route to unsymmetrically substituted bisphosphinoureas − and a novel chirality pattern for their complexes, both in the solid state and in solution. With the establishment of the chiral solid-state structure for ( R , S ) A2 ‘ -[Pd(κ 2 - P , P -{P(OC 6 H 3 Bu t 2 -2,4) 2 N(Me)C(O)N(Me)PPh 2 }Cl 2 ] ( 1 ) 4 that prevails in solution and can also be observed for cis -[Mo(CO) 4 {P(OC 6 H 3 Bu t 2 -2,4) 2 N(Me)CON(Me)PPh 2 } 2 ] ( 2 ), it became apparent that chirality is likely to be a general feature of all folded bisphosphinourea transition-metal complexes.…”
The title compound [(kappa2-P,P-[PPh(2)NMe}2CO)Cu(I)Cl]2 (4) is readily formed by the reaction between (PPh2NMe)2CO and copper(I) chloride. Compound 4 forms a two-dimensional supramolecular network of Cu2Cl2-centered dimers that are linked by pi-pi interaction between the phenyl substituents on phosphorus in the solid state. Because of the nature of these pi-pi interactions, only one of the three possible enantiomers, the meso form, can be observed in the crystals.
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