Neutral stibinyl and bismuthinyl radicals are typically short-lived, reactive species. Here we show the synthesis and solid-state structures of two stable stibinyl L(Cl)Ga
Sb· 1 and bismuthinyl ...radicals L(I)Ga
Bi· 4, which are stabilized by electropositive metal centers. Their description as predominantly metal-centered radicals is consistent with the results of NMR, EPR, SQUID, and DFT studies. The Lewis-acidic character of the Ga ligands allow for significant electron delocalization of the Sb- and Bi- unpaired radical onto the ligand. Single-electron reduction of L(Cl)Ga
Sb· gave LGaSbGa(Cl)L 5, the first compound containing a Ga=Sb double bond. The π-bonding contribution is estimated to 9.56 kcal mol
by NMR spectroscopy. The bonding situation and electronic structure is analyzed by quantum mechanical computations, revealing significant π backdonation from the Sb to the Ga atom. The formation of 5 illustrates the high-synthetic potential of 1 for the formation of new compounds with unusual electronic structures.
Two equivalents of LGa (L=HCC(Me)N(2,6‐iPr2C6H3)2) reacted with PX3 (X=Cl, Br) with insertion into two P−X bonds and formation of L(X)Ga2PX (X=Cl 1, Br 2), whereas the analogous reaction with AsCl3 ...occurred with twofold insertion and subsequent elimination of LGaCl2 and formation of the Ga‐substituted diarsene L(Cl)Ga2As2 (3). Analogous findings were observed in the reactions with Me2NAsCl2, yielding the unsymmetrically‐substituted diarsene L(Cl)GaAs=AsGa(NMe2)L (4). The reaction of As(NMe2)3 with LGa gave L(Me2N)Ga2As2 (5) after heating at 165 °C for five days, whereas the reaction with LAl gave L(Me2N)Al2As2 (6) after heating at only 80 °C for one day. Finally, two equivalents of LGa reacted with Bi(NEt2)3 to give L(Et2N)Ga2Bi2 (7). Complexes 1–7 were characterized by NMR spectroscopy (1H, 13C, 31P), elemental analysis, and single‐crystal X‐ray diffraction (except for 1 and 5). The bonding situations in 4, 6, and 7 were analyzed by quantum chemical calculations.
Complex chemistry: LGa reacted with PX3 with formation of L(X)Ga2PX (X=Cl, Br; L=HCC(Me)N(2,6‐iPr2C6H3)2), whereas reactions with AsCl3, Me2NAsCl2, As(NMe2)3, and Bi(NEt2)3 yielded Ga‐substituted dipnictenes L(Cl)Ga2As2, L(Cl)GaAs2Ga(NMe2)L, L(Me2N)Ga2As2, and L(Et2N)Ga2Bi2. Quantum chemical calculations revealed the bonding situation within the complexes.
This conceptual paper seeks to clarify the process of the emergence of positive collective affect. Specifically, it develops a dynamic model of the emergence of positive affective similarity in work ...groups. It is suggested that positive group affective similarity and within-group relationship quality are reciprocally interrelated in the form of a self-reinforcing spiral, which is driven by mechanisms of affective sharing and affective similarity-attraction between group members. We label this spiraling relationship 'Positive Group Affect Spiral.' This spiral is proposed to continuously strengthen both the similarity of group members' positive affect and the quality of their interpersonal relationships in a dynamic process. Further, we embed the Positive Group Affect Spiral into a framework of contextual factors that may diminish or strengthen its functioning, considering the potential impacts of charismatic leadership, individuals' or subgroups' organizational cynicism, group and organizational emotion norms, and organizational identity.
The novel coordination polymer Eu(O
2
CCF
3
)
2
(dmf)
2
∞
(
1
) (dmf =
N
,
N
-dimethylformamide) containing europium(
ii
) and the two new compounds (NH
4
)
2
Eu
6
F
8
(O
2
CCF
3
)
12
(CF
3
COOH)
6
...(
2
) and (NH
4
)
2
Eu
6
F
8
(O
2
CC
2
F
5
)
12
(C
2
F
5
COOH)
6
·8C
2
F
5
COOH (
3
), both based on hexanuclear europiate(
iii
) complexes, were synthesized from precursors with a Eu
2+
: Eu
3+
ratio >1, obtained by reaction of europium metal with ammonium perfluorocarboxylates in liquid ammonia. In the crystal structure of
1
the europium(
ii
) ions are bridged by carboxylate groups and
N
,
N
-dimethylformamide to form polymeric chains with Eu
2+
Eu
2+
distances of 408.39(13)-410.49(13) pm. The compound crystallizes in the triclinic space group
P
1&cmb.macr; (
Z
= 2). To the best of our knowledge, this is the first example of a (solvated) perfluorocarboxylate containing a lanthanoid in a subvalent oxidation state. In the crystal structures of
2
and
3
the europium(
iii
) ions are bridged by fluoride ions and carboxylate groups to form hexanuclear complex anions with an octahedral arrangement of the cations. The Eu
3+
Eu
3+
distances are in the range of 398.27(15)-400.93(15) pm in
2
and 395.37(4)-399.78(5) pm in
3
, respectively. Both compounds crystallize in the monoclinic space group type
P
2
1
/
n
(
Z
= 4) and are the first examples of
octahedro
-hexanuclear europium carboxylates for which fluoride is reported as a bridging ligand. In all compounds the oxidation state of europium was monitored
via
151
Eu Mössbauer and photoluminescene spectroscopy.
This work introduces the first europium(
ii
) perfluorocarboxylate and the use of its class of compounds in the facile synthesis of
octahedro
-hexanuclear europium(
iii
) fluoridocarboxylates with interesting luminophoric properties.
For much of the 20th century, American gays and lesbians lived in fear that public exposure of their sexualities might cause them to be fired, blackmailed, or even arrested. Today, they are enjoying ...an unprecedented number of legal rights and protections. Clearly, the tides have shifted for gays and lesbians, but what caused this enormous sea change?
In his gripping new book, Walter Frank offers an in-depth look at the court cases that were pivotal in establishing gay rights. But he also tells the story of those individuals who were willing to make waves by fighting for those rights, taking enormous personal risks at a time when the tide of public opinion was against them. Frank’s accessible style brings complex legal issues down to earth but, as a former litigator, never loses sight of the law’s human dimension and the context of the events occurring outside the courtroom.
Chronicling the past half-century of gay and lesbian history, Law and the Gay Rights Story offers a unique perspective on familiar events like the Stonewall Riots, the AIDS crisis, and the repeal of “Don’t Ask, Don’t Tell.” Frank pays special attention to the constitutional issues surrounding same-sex marriage and closely analyzes the two recent Supreme Court cases addressing the issue. While a strong advocate for gay rights, Frank also examines critiques of the movement, including some coming from the gay community itself. Comprehensive in coverage, the book explains the legal and constitutional issues involved in each of the major goals of the gay rights movement: a safe and healthy school environment, workplace equality, an end to anti-gay violence, relationship recognition, and full integration into all the institutions of the larger society, including marriage and military service. Drawing from extensive archival research and from decades of experience as a practicing litigator, Frank not only provides a vivid history, but also shows where the battle for gay rights might go from here.
The present study examines the association between dysfunctional team behavior and team performance. Data included measures of teams' dysfunctional behavior and negative affective tone as well as ...supervisors' ratings of teams' (nonverbal) negative emotional expressivity and performance. Utilizing a field sample of 61 work teams, the authors tested the proposed relationships with robust data analytic techniques. Results were consistent with the hypothesized conceptual scheme, in that negative team affective tone mediated the relationship between dysfunctional team behavior and performance when teams' nonverbal negative expressivity was high but not when nonverbal expressivity was low. On the basis of the findings, the authors conclude that the connection between dysfunctional behavior and performance in team situations is more complex than was previously believed-thereby yielding a pattern of moderated mediation. In sum, the findings demonstrated that team members' collective emotions and emotional processing represent key mechanisms in determining how dysfunctional team behavior is associated with team performance.
Although research has long focused on the consequences of leaders’ charismatic behavior, the antecedents of such leadership are increasingly gaining scholarly attention. Nevertheless, the ...antecedent-oriented literature on charismatic leadership has been fragmented to date and lacks theoretical integration. Also, important gaps remain within this developing line of inquiry. Therefore, this article systematically reviews extant research on charismatic leadership behavior emergence and advances a more comprehensive perspective by integrating previous work into an overall conceptual framework. Building on these considerations, the authors outline potentially fruitful directions for future research.
In this report, two distinctive intramolecular cyclizations of o‐propargyloxy diketopiperazines (achieved from a one‐pot Ugi post‐transformation) is achieved via a copper(I)‐catalyzed intramolecular ...reaction of azomethine ylide and alkyne moiety. The presence of internal alkyne in the starting materials directed the reaction towards through 3+2‐cycloaddition, while terminal alkyne led to a spirocyclization reaction between azomethine ylide and terminal unsaturated C−C bond. This method offering an opportunity for the synthesis of challenging Diazabicyclics and Spiro‐Diketopiperazinochromanes in high yields with exclusive diastereoselectivity.
This research examines how the implications of emotional labor can transfer from customer encounters to coworker interactions using temporally lagged data from a sample of frontline service ...employees. The results show that surface acting in customer service encounters is positively, and deep acting is negatively, related to ego depletion. Employees’ ego depletion, in turn, is positively associated with their interpersonally harmful behavior toward coworkers. Hence, ego depletion appears as a mediating variable that translates the implications of distinct emotional labor strategies into coworker harming. Moreover, emotion regulation self‐efficacy moderates the role of surface acting. The positive indirect relationship between surface acting and coworker harming, via ego depletion, is buffered among employees with higher emotion regulation self‐efficacy. These findings shed new light on the complex and far‐reaching consequences of emotional labor. We demonstrate the relevance of emotional labor to third parties not directly involved in customer service encounters and highlight important mediators and boundary conditions of these indirect relations.
There are two Food and Drug Administration (FDA)-approved antivenoms available for rattlesnake envenomations in the United States: the equine-derived F (ab’)2 product sold with the brand name Anavip ...(F (ab')2 AV) and the ovine-derived Fab product sold with the brand name Crofab (FabAV).
To compare the clinical outcomes of rattlesnake envenomation patients treated either with FabAV or F (ab')2AV or a combination of these.
This is a retrospective chart review of all human rattlesnake envenomations requiring antivenom reported to one regional poison control center in 2019. Patients were categorized as receiving F (ab')2 AV, FabAV, or a combination of both. Baseline characteristics included demographics, time between envenomation and administering antivenom, an abbreviated snakebite severity score (ASSS), and the presence of coagulopathy at presentation.
There were a total of 123 patients requiring antivenom. Of these, 57 (46.3%) received FabAV, 53 (43.1%) received F (ab')2 AV, and 13 (10.6%) received a combination of these. Those receiving F (ab')2 AV were younger, with an average age of 40.8 (±25.0) years versus 51.3 (±19.9) years (p = 0.0161) for those receiving FabAV. Time between envenomation and antivenom administration, ASSS, and the percentage of those with coagulopathy at presentation were otherwise similar. Patients treated with F (ab')2 AV or FabAV received a similar total number of vials 16.0 vials (±6.1) vs 14.5 vials (±5.4), p = 0.189, but patients treated with F (ab')2 AV were more frequently given additional doses 31 patients (58.5%) vs. 22 FabAV patients (38.6%), p = 0.0051. In patients with outpatient follow-up for 2 weeks, fewer patients treated with F (ab')2 AV developed late coagulopathy 5 patients (11.1%) vs 22 FabAV patients (48.9%), p = 0.0004. Adverse events were generally mild and uncommon with no difference in frequency between patients who received either antivenom (2 F (ab')2 AV patients vs 4 FabAV patients, p = 0.6637).
Other than patient age, we found no significant difference in the baseline demographics, time between envenomation and administering antivenom, an abbreviated snakebite severity score (ASSS), and the presence of coagulopathy at presentation between patients receiving F (ab')2 AV or FabAV. Patients receiving F (ab')2 AV were more likely to be given an additional dose beyond the minimum typical treatment course, but less likely to develop late coagulopathy. Adverse events were uncommon and generally mild whether patients received either antivenom.
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•A comparison of Fab and an F (ab’)2 rattlesnake antivenom in the United States.•Patients treated with either antivenom received a similar total number of vials.•Fewer patients treated with F (ab')2 antivenom developed late coagulopathy.•Adverse events were generally mild and uncommon with both antivenoms.
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